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Sample records for hydrotreating process kinetics

  1. Process developments in gasoil hydrotreating

    Energy Technology Data Exchange (ETDEWEB)

    Lawrence, R.C.; Kinley, D.H.; Wood, M.A. [Davy Process Technology Limited, London (United Kingdom)

    1997-07-01

    Changing demand patterns and legislation increase the pressure upon hydrotreating capacities at many refineries. To meet these pressures, improvements have been and will be necessary not only in catalysts, but also in the hydrotreating process. On the basis of its hydrogenation experience, Davy Process Technology has developed and tested a number of concepts aimed at improving the effectiveness of the basic process - enabling economic deep desulfurisation and opening up the potential for an integrated HDS/HDA flowsheet using sulphur tolerant HDA Catalysts.

  2. Green Diesel from Hydrotreated Vegetable Oil Process Design Study

    NARCIS (Netherlands)

    Hilbers, T.J.; Sprakel, Lisette Maria Johanna; van den Enk, L.B.J.; Zaalberg, B.; van den Berg, Henderikus; van der Ham, Aloysius G.J.

    2015-01-01

    A systematic approach was applied to study the process of hydrotreating vegetable oils. During the three phases of conceptual, detailed, and final design, unit operations were designed and sized. Modeling of the process was performed with UniSim Design®. Producing green diesel and jet fuel from

  3. Experimental and kinetics studies of aromatic hydrogenation in a two-stage hydrotreating process using NiMo/Al{sub 2}O{sub 3} and NiW/Al{sub 2}O{sub 3} catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Owusu-Boakye, A.; Dalai, A.K.; Ferdous, D. [Saskatchewan Univ., Saskatoon, SK (Canada). Dept. of Chemical Engineering, Catalysis and Chemical Reaction Engineering Laboratories; Adjaye, J. [Syncrude Canada Ltd., Edmonton, AB (Canada)

    2006-10-15

    The degree of hydrogenation of aromatics in light gas oil (LGO) feed from Athabasca bitumen was examined using a two-stage process. Experiments were conducted in a trickle-bed reactor using 2 catalysts, namely nickel molybdenum alumina (NiMo/Al{sub 2}O{sub 3}) in stage one and nickel tungsten alumina (NiW/Al{sub 2}O{sub 3}) in the second stage. NiMo/Al{sub 2}O{sub 3} was used in the first stage in order to remove nitrogen and sulphur containing heteroatoms. NiW/Al{sub 2}O{sub 3} was used in the second stage for saturation of the aromatic rings in the hydrocarbon species. The catalysts were used under a range of temperature and pressure condition. Temperature and liquid hourly space velocity ranged from 350 to 390 degrees C and 1.0 to 1.5 per hour, respectively. Pressure was kept constant at 11.0 MPa for all experiments. Reaction time results from the two-stage process were compared with those from a single-stage where hydrotreating was performed over NiMo/AL{sub 2}O{sub 3}. Product samples from different feedstocks were analyzed with respect to sulfur, nitrogen and aromatic content. Gasoline selectivity and kinetic parameters for hydrodesulphurization (HDS) or hydrodenitrogenation (HDN) reactions for the feed materials were also compared. The effect of hydrogen sulphide (H{sub 2}S) inhibition on aromatics hydrogenation (HDA) was also kinetically modelled using the Langmuir-Hinshelwood approach. Kinetic analysis of the single-stage hydrotreating process showed that HDA and HDS activities were slowed by the presence of hydrogen sulphide that is produced as a by-product of the HDS process. However, with inter-stage removal of hydrogen sulphide in the two-stage process, significant improvement of the HDA and HDS activities were noted. It was concluded that the experimental data was successfully predicted by the Langmuir-Hinshelwood kinetic models. 27 refs., 4 tabs., 8 figs.

  4. Syntheses, Characterization and Kinetics of Nickel-Tungsten Nitride Catalysts for Hydrotreating of Gas Oil

    Science.gov (United States)

    Botchwey, Christian

    This thesis summarizes the methods and major findings of Ni-W(P)/gamma-Al 2O3 nitride catalyst synthesis, characterization, hydrotreating activity, kinetic analysis and correlation of the catalysts' activities to their synthesis parameters and properties. The range of parameters for catalyst synthesis were W (15-40 wt%), Ni (0-8 wt%), P (0-5 wt%) and nitriding temperature (TN) (500-900 °C). Characterization techniques used included: N2 sorption studies, chemisorption, elemental analysis, temperature programmed studies, x-ray diffraction, scanning electron microscopy, energy dispersive x-ray, infrared spectroscopy, transmission electron microscopy and x-ray absorption near edge structure. Hydrodesulfurization (HDS), hydrodenitrogenation (HDN) and hydrodearomatization (HDA) were performed at: temperature (340-380 °C), pressure (6.2-9.0 MPa), liquid hourly space velocity (1-3 h-1) and hydrogen to oil ratio (600 ml/ml, STP). The predominant species on the catalyst surface were Ni3N, W2N and bimetallic Ni2W3N. The bimetallic Ni-W nitride species was more active than the individual activities of the Ni3N and W2N. P increased weak acid sites while nitriding temperature decreased amount of strong acid sites. Low nitriding temperature enhanced dispersion of metal particles. P interacted with Al 2O3 which increased the dispersion of metal nitrides on the catalyst surface. HDN activity increased with Ni and P loading but decreased with increase in nitriding temperature (optimum conversion; 60 wt%). HDS and HDA activities went through a maximum with increase in the synthesis parameters (optimum conversions; 88. wt% for HDS and 47 wt% for HDA). Increase in W loading led to increase in catalyst activity. The catalysts were stable to deactivation and had the nitride structure conserved during hydrotreating in the presence of hydrogen sulfide. The results showed good correlation between hydrotreating activities (HDS and HDN) and the catalyst nitrogen content, number of exposed

  5. Improving fuel quality by whole crude oil hydrotreating: A kinetic model for hydrodeasphaltenization in a trickle bed reactor

    International Nuclear Information System (INIS)

    Jarullah, A.T.; Mujtaba, I.M.; Wood, A.S.

    2012-01-01

    Highlights: ► Asphaltene contaminant must be removed to a large extent from the fuel to meet the regulatory demand. ► Kinetics for hydrodeasphaltenization are estimated via experimentation and modeling. ► Using the kinetic parameters, a full process model for the trickle bed reactor (TBR) is developed. ► The model is used for simulating the behavior of the TBR to get further insight of the process. ► The influences of operating conditions in the hydrodeasphaltenization process are reported. -- Abstract: Fossil fuel is still a predominant source of the global energy requirement. Hydrotreating of whole crude oil has the ability to increase the productivity of middle distillate fractions and improve the fuel quality by simultaneously reducing contaminants such as sulfur, nitrogen, vanadium, nickel and asphaltene to the levels required by the regulatory bodies. Hydrotreating is usually carried out in a trickle bed reactor (TBR) where hydrodesulfurization (HDS), hydrodenitrogenation (HDN), hydrodemetallization (HDM) and hydrodeasphaltenization (HDAs) reactions take place simultaneously. To develop a detailed and a validated TBR process model which can be used for design and optimization of the hydrotreating process, it is essential to develop kinetic models for each of these reactions. Most recently, the authors have developed kinetic models for all of these chemical reactions except that of HDAs. In this work, a kinetic model (in terms of kinetic parameters) for the HDAs reaction in the TBR is developed. A three phase TBR process model incorporating the HDAs reactions with unknown kinetic parameters is developed. Also, a series of experiments has been conducted in an isothermal TBR under different operating conditions affecting the removal of asphaltene. The unknown kinetic parameters are then obtained by applying a parameter estimation technique based on minimization of the sum of square errors (SSEs) between the experimental and predicted concentrations of

  6. Studies on catalytic hydrotreating of recycled solvents from coal liquefaction process. Part 1. Characteristics changes of recycled solvents during hydrotreating

    Energy Technology Data Exchange (ETDEWEB)

    Morimura, Y.; Nakata, S.; Yokota, Y.; Shirota, Y.; Nakamura, M. [Chiyoda Corp., Tokyo (Japan); Mitarai, Y. [Sumitomo Metal Mining Co. Ltd., Tokyo (Japan); Inoue, Y. [Nippon Ketjen Co. Ltd., Tokyo (Japan)

    1995-07-01

    A bituminous coal liquefaction process, called the NEDOL process, is under development by the New Energy and Industrial Technology Development Organization (NEDO). Important features of this process include the capacity to produce hydrogen-donatable solvents, obtained by hydrogenation of middle distillates of coal derived oils, and to recycle these solvents to a liquefaction stage as hydrogen donor solvents. These recycled solvents, obtained by liquefaction of Wandoan coal, and their catalytic hydrotreated oils, have been extensively characterized, using a variety of analytical methods. The following items have been examined and are discussed in this study: (1) Influence of chemical hydrogen consumption on the reactivities of hydrodesulfurization (HDS), hydrodenitrogenation (HDN), hydrodeoxygenation (HDO) and hydrogenation of aromatic-rings, during hydrotreating; (2) Changes in composition of hydrocarbon types, nitrogen- and oxygen-containing compounds, as a function of chemical hydrogen consumption; (3) Changes of average molecular weights; (4) Characteristics changes of oxygen- and nitrogen-containing compounds, and reactivities of HDO and HDN; (5) Characteristics changes of donatable hydrogen as a function of a degree of hydrogenation ({delta}fa). 14 refs., 14 figs., 3 tabs.

  7. Studies on Hydrotreating Process of Microcrystalline Wax Produced from Marine Belayim Crude Oil

    International Nuclear Information System (INIS)

    EI Karashi, S.; Marawan, H.

    2004-01-01

    Abstract Microcrystalline wax was produced from solvent dewaxing process of vacuum residue raffinate produced from Marine Belayim origin. The untreated microcrystalline wax contains trace amounts of sulfur, oxygen, nitrogen and organometallic compounds as well as heavy aromatics which affect the properties of wax applications in pharmaceutical and technical fields . Microcrystalline wax hydrotreating process was studied using digital controlled unit and Ni O-MoO 3 / Al 2 O 3 catalyst, where operating parameters that controlled the efficiency of the hydrotreated wax were studied separately at different values including reactor temperature, reactor pressure, liquid hourly space velocity and hydrogen to hydrocarbon ratio . Hydrotreated microcrystalline wax at operating conditions (temperature 300 degree C, pressure 73 kg/cm 2 , LHS V 0.52 h-l and H 2 /HC ratio 266.6 Nm 3 /m 3 ) has the best quality to be used as food grade wax

  8. A study on the hydrotreating of coal hydro liquefaction residue and its kinetics

    Energy Technology Data Exchange (ETDEWEB)

    Huang, J.; Lu, X.; Zhang, D.; Gao, J. [Department of Chemical Engineering for Energy Resources, East China University of Science and Technology, Shanghai (China)

    2010-09-15

    Hydro-conversion of coal hydro liquefaction residue obtained from a 6 t/day pilot plant of Shenhua Group in Shanghai was carried out under the hydrotreating condition. The coal hydro liquefaction residue and its product were extracted in sequence with n-hexane, toluene and tetrahydrofuran in a Soxhlet apparatus. The n-hexane soluble fractions increased with the increase of reaction temperature and time. Its amount increased from 14.14% to a maximum of 40.86% under the conditions of 470 {sup o}C and 30 min, which meant that moderate extension of coal residence time in the coal hydro liquefaction reactor is beneficial to the increase of oil yield. A 4-lumped kinetic model of coal hydro liquefaction residue hydro-conversion was performed using solubility-based lumped fractions. In the model, the tetrahydrofuran insoluble fractions were classified into two parts: easily reactive part and unreactive part. The kinetic parameters were estimated by a fourth-order Runge-Kutta method and a nonlinear least squares method, and the apparent activation energies were calculated according to the Arrhenius Equation. A large quantity of total catalyst consisting of remained liquefaction catalyst, part of the mineral from raw coal and additive Fe-based catalyst could considerably reduce the apparent activation energy of hydro-conversion for the toluene insoluble/tetrahydrofuran insoluble fractions to 36.79 kJ-mol{sup -1}. The calculated values of the model coincided well with the experimental values. (authors)

  9. A Study on the Hydrotreating of Coal Hydroliquefaction Residue and its Kinetics

    Directory of Open Access Journals (Sweden)

    Jinsheng Gao

    2010-09-01

    Full Text Available Hydro-conversion of coal hydroliquefaction residue obtained from a 6t/day pilot plant of Shenhua Group in Shanghai was carried out under the hydrotreating condition. The coal hydroliquefaction residue and its product were extracted in sequence with n-hexane, toluene and tetrahydrofuran in a Soxhlet apparatus. The n-hexane soluble fractions increased with the increase of reaction temperature and time. Its amount increased from 14.14% to a maximum of 40.86% under the conditions of 470 °C and 30 min, which meant that moderate extension of coal residence time in the coal hydroliquefaction reactor is beneficial to the increase of oil yield. A 4-lumped kinetic model of coal hydroliquefaction residue hydro-conversion was performed using solubility-based lumped fractions. In the model, the tetrahydrofuran insoluble fractions were classified into two parts: easily reactive part and unreactive part. The kinetic parameters were estimated by a fourth-order Runge-Kutta method and a nonlinear least squares method, and the apparent activation energies were calculated according to the Arrhenius Equation. A large quantity of total catalyst consisting of remained liquefaction catalyst, part of the mineral from raw coal and additive Fe-based catalyst could considerably reduce the apparent activation energy of hydro-conversion for the toluene insoluble/tetrahydrofuran insoluble fractions to 36.79 kJ•mol-1. The calculated values of the model coincided well with the experimental values.

  10. Analysis of the reactivity of sulphur compounds in petroleum cuts: kinetics and modelling of hydro-treating; Analyse de la reactivite des composes soufres dans les coupes petrolieres: cinetique et modelisation de l'hydrotraitement

    Energy Technology Data Exchange (ETDEWEB)

    Lopez Garcia, C

    2000-12-01

    The study of the hydro-treating of middle distillates comprised the following steps: - Identification and reactivity study of the sulphur compounds present in these petroleum cuts; - Modelling of the process by a chemical kinetic approach. The hydro-treating of middle distillates is a refining process that allows elimination of organic compounds containing sulphur, nitrogen, oxygen and metals. The process also hydrogenates the aromatic compounds providing improved cetane index gas-oils while respecting the regulations that severely limit the content of sulphur compounds. The extension and the improvement of a kinetic model for the hydro-treating of LCO gas-oils (light cycle oil gas-oils) are presented in this work. In order to improve the hydro-desulfurization model predictions, a detailed identification of the sulphur compounds contained in LCO gas-oils was carried out using gas chromatography with a sulphur chemiluminescence detector (GC-SCD). The most refractory sulphur compounds (alkyl-di-benzothiophenes) were identified and lumped into different families. Based on a lumped reaction scheme with a Langmuir-Hinshelwood representation, the model takes into account the influence of temperature, total pressure and hydrogen sulphide partial pressure on the reaction rates for hydro-desulfurization, hydro-denitrogenation and hydro-de-aromatization. The model parameter estimation was based on experiments that were carried out on a micro-pilot unit using an industrial sulfided NiMo/Al{sub 2}O{sub 3} catalyst and LCO feedstocks. The analytical study of the sulphur compounds was also extended to the case of straight run gas-oils (SR). For these feedstocks, a method using high-resolution mass spectrometry coupled with gas chromatography (GC-HRMS) was developed. In this way, the kinetic model can now be extended for the SR gas-oil hydro-treating or for LCO-SR mixtures. (author)

  11. Analysis of the reactivity of sulphur compounds in petroleum cuts: kinetics and modelling of hydro-treating; Analyse de la reactivite des composes soufres dans les coupes petrolieres: cinetique et modelisation de l'hydrotraitement

    Energy Technology Data Exchange (ETDEWEB)

    Lopez Garcia, C.

    2000-12-01

    The study of the hydro-treating of middle distillates comprised the following steps: - Identification and reactivity study of the sulphur compounds present in these petroleum cuts; - Modelling of the process by a chemical kinetic approach. The hydro-treating of middle distillates is a refining process that allows elimination of organic compounds containing sulphur, nitrogen, oxygen and metals. The process also hydrogenates the aromatic compounds providing improved cetane index gas-oils while respecting the regulations that severely limit the content of sulphur compounds. The extension and the improvement of a kinetic model for the hydro-treating of LCO gas-oils (light cycle oil gas-oils) are presented in this work. In order to improve the hydro-desulfurization model predictions, a detailed identification of the sulphur compounds contained in LCO gas-oils was carried out using gas chromatography with a sulphur chemiluminescence detector (GC-SCD). The most refractory sulphur compounds (alkyl-di-benzothiophenes) were identified and lumped into different families. Based on a lumped reaction scheme with a Langmuir-Hinshelwood representation, the model takes into account the influence of temperature, total pressure and hydrogen sulphide partial pressure on the reaction rates for hydro-desulfurization, hydro-denitrogenation and hydro-de-aromatization. The model parameter estimation was based on experiments that were carried out on a micro-pilot unit using an industrial sulfided NiMo/Al{sub 2}O{sub 3} catalyst and LCO feedstocks. The analytical study of the sulphur compounds was also extended to the case of straight run gas-oils (SR). For these feedstocks, a method using high-resolution mass spectrometry coupled with gas chromatography (GC-HRMS) was developed. In this way, the kinetic model can now be extended for the SR gas-oil hydro-treating or for LCO-SR mixtures. (author)

  12. Modelling of the Kinetics of Sulfure Compounds in Desulfurisation Processes Based on Industry Data of Plant

    Directory of Open Access Journals (Sweden)

    Krivtcova Nadezhda

    2016-01-01

    Full Text Available Modelling of sulfur compounds kinetics was performed, including kinetics of benzothiophene and dibenzothiophene homologues. Modelling is based on experimental data obtained from monitoring of industrial hydrotreating set. Obtained results include kinetic parameters of reactions.

  13. Modelling of the Kinetics of Sulfure Compounds in Desulfurisation Processes Based on Industry Data of Plant

    OpenAIRE

    Krivtsova, Nadezhda Igorevna; Tataurshikov, A.; Kotkova, Elena

    2016-01-01

    Modelling of sulfur compounds kinetics was performed, including kinetics of benzothiophene and dibenzothiophene homologues. Modelling is based on experimental data obtained from monitoring of industrial hydrotreating set. Obtained results include kinetic parameters of reactions.

  14. Deep hydrotreating of middle distillates from crude and shale oils

    Energy Technology Data Exchange (ETDEWEB)

    Landau, M.V. [The Blechner Center for Industrial Catalysis and Process Development, Ben-Gurion University of the Negev, Beer-Sheva (Israel)

    1997-06-20

    The potential scientific and technological solutions to the problems that appear as a result of shifting the hydrotreating of crude oil middle distillates and shale oils from the `normal` to the `deep` mode are considered on the basis of the reactivities and transformation routes of the least-reactive sulfur-, nitrogen-, and oxygen-containing compounds. The efficiency of selecting the optimal feedstock, increasing the process severity, improving the catalysts activity, and using alternative catalytic routes are compared, taking into account the specific issues related to deep hydrodesulfurization/hydrodenitrogenation/hydrodeoxygenation, i.e., chemical aspects, kinetics and catalysts

  15. Irreversible processes kinetic theory

    CERN Document Server

    Brush, Stephen G

    2013-01-01

    Kinetic Theory, Volume 2: Irreversible Processes deals with the kinetic theory of gases and the irreversible processes they undergo. It includes the two papers by James Clerk Maxwell and Ludwig Boltzmann in which the basic equations for transport processes in gases are formulated, together with the first derivation of Boltzmann's ""H-theorem"" and a discussion of this theorem, along with the problem of irreversibility.Comprised of 10 chapters, this volume begins with an introduction to the fundamental nature of heat and of gases, along with Boltzmann's work on the kinetic theory of gases and s

  16. Trickle bed reactor model to simulate the performance of commercial diesel hydrotreating unit

    Energy Technology Data Exchange (ETDEWEB)

    C. Murali; R.K. Voolapalli; N. Ravichander; D.T. Gokak; N.V. Choudary [Bharat Petroleum Corporation Ltd., Udyog Kendra (India). Corporate R& amp; D Centre

    2007-05-15

    A two phase mathematical model was developed to simulate the performance of bench scale and commercial hydrotreating reactors. Major hydrotreating reactions, namely, hydrodesulphurization, hydrodearomatization and olefins saturation were modeled. Experiments were carried out in a fixed bed reactor to study the effect of different process variables and these results were used for estimating kinetic parameters. Significant amount of feed vaporization (20-50%) was estimated under normal operating conditions of DHDS suggesting the importance of considering feed vaporization in DHDS modeling. The model was validated with plant operating data, under close to ultra low sulphur levels by correctly accounting for feed vaporization in heat balance relations and appropriate use of hydrodynamic correlations. The model could predict the product quality, reactor bed temperature profiles and chemical hydrogen consumption in commercial plant adequately. 14 refs., 7 figs., 6 tabs.

  17. Regeneration of Hydrotreating and FCC Catalysts

    Energy Technology Data Exchange (ETDEWEB)

    CM Wai; JG Frye; JL Fulton; LE Bowman; LJ Silva; MA Gerber

    1999-09-30

    Hydrotreating, hydrocracking, and fluid catalytic cracking (FCC) catalysts are important components of petroleum refining processes. Hydrotreating and hydrocracking catalysts are used to improve the yield of high-quality light oil fractions from heavier crude oil and petroleum feedstocks containing high levels of impurities. FCC catalysts improve the yield of higher octane gasoline from crude oil. Residuum hydrotreating and cracking catalysts are susceptible to irreversible deactivation caused by adsorption of sulfur and by metals impurities, such as vanadium and nickel. The gradual buildup of these impurities in a hydrotreating catalyst eventually plugs the pores and deactivates it. Nickel and vanadium adversely affect the behavior of cracking catalysts, reducing product yield and quality. Replacing deactivated catalysts represents a significant cost in petroleum refining. Equally important are the costs and potential liabilities associated with treating and disposing spent catalysts. For example, recent US Environmental Protection Agency rulings have listed spent hydrotreating and hydrorefining catalysts as hazardous wastes. FCC catalysts, though more easily disposed of as road-base or as filler in asphalt and cement, are still an economic concern mainly because of the large volumes of spent catalysts generated. New processes are being considered to increase the useful life of catalysts or for meeting more stringent disposal requirements for spent catalysts containing metals. This report discusses a collaborative effort between Pacific Northwest National Laboratory (PNNL) and Phillips Petroleum, Inc., to identify promising chemical processes for removing metals adhered to spent hydrodesulfurization (HDS, a type of hydrotreating catalyst) and FCC catalysts. This study, conducted by PNNL, was funded by the US Department of Energy's Bartlesville Project Office. Fresh and spent catalysts were provided by Phillips Petroleum. The FCC catalyst was a rare

  18. Rejuvenation of residual oil hydrotreating catalysts by leaching of foulant metals. Modelling of the metal leaching process

    Energy Technology Data Exchange (ETDEWEB)

    Marafi, M.; Kam, E.K.T.; Stanislaus, A.; Absi-Halabi, M. [Petroleum Technology Department, Petroleum, Petrochemicals and Materials Division, Kuwait Institute for Scientific Research, Safat (Kuwait)

    1996-11-19

    Increasing emphasis has been paid in recent years on the development of processes for the rejuvenation of spent residual oil hydroprocessing catalysts, which are deactivated by deposition of metals (e.g. vanadium) and coke. As part of a research program on this subject, we have investigated selective removal of the major metal foulant from the spent catalyst by chemical leaching. In the present paper, we report the development of a model for foulant metals leaching from the spent catalyst. The leaching process is considered to involve two consecutive operations: (1) removal of metal foulants along the main mass transfer channels connected to the narrow pores until the pore structure begins to develop and (2) removal of metal foulants from the pore structure. Both kinetic and mass transfer aspects were considered in the model development, and a good agreement was noticed between experimental and simulated results

  19. Hydrotreating of coal-derived liquids

    Energy Technology Data Exchange (ETDEWEB)

    Lott, S.E.; Stohl, F.V.; Diegert, K.V. [Sandia National Lab., Albuquerque, NM (United States)] [and others

    1995-12-31

    To develop a database relating hydrotreating parameters to feed and product quality by experimentally evaluating options for hydrotreating whole coal liquids, distillate cuts of coal liquids, petroleum, and blends of coal liquids with petroleum.

  20. Reuse of Hydrotreating Spent Catalyst

    International Nuclear Information System (INIS)

    Habib, A.M.; Menoufy, M.F.; Amhed, S.H.

    2004-01-01

    All hydro treating catalysts used in petroleum refining processes gradually lose activity through coking, poisoning by metal, sulfur or halides or lose surface area from sintering at high process temperatures. Waste hydrotreating catalyst, which have been used in re-refining of waste lube oil at Alexandria Petroleum Company (after 5 years lifetime) compared with the same fresh catalyst were used in the present work. Studies are conducted on partial extraction of the active metals of spent catalyst (Mo and Ni) using three leaching solvents,4% oxidized oxalic acid, 10% aqueous sodium hydroxide and 10% citric acid. The leaching experiments are conducting on the de coked extrude [un crushed] spent catalyst samples. These steps are carried out in order to rejuvenate the spent catalyst to be reused in other reactions. The results indicated that 4% oxidized oxalic acid leaching solution gave total metal removal 45.6 for de coked catalyst samples while NaOH gave 35% and citric acid gave 31.9 % The oxidized leaching agent was the most efficient leaching solvent to facilitate the metal removal, and the rejuvenated catalyst was characterized by the unchanged crystalline phase The rejuvenated catalyst was applied for hydrodesulfurization (HDS) of vacuum gas oil as a feedstock, under different hydrogen pressure 20-80 bar in order to compare its HDS activity

  1. Sulfur and octane trade off in FCC naphta conventional hydrotreating

    Energy Technology Data Exchange (ETDEWEB)

    Badra, C. [INTEVEP S.A. Research and Technological Support Center of Petroleos de Venzuela, Caracas (Venezuela). Dept. de Refinacion; Perez, J.A. [INTEVEP S.A. Research and Technological Support Center of Petroleos de Venzuela, Caracas (Venezuela). Dept. de Refinacion; Salazar, J.A. [INTEVEP S.A. Research and Technological Support Center of Petroleos de Venzuela, Caracas (Venezuela). Dept. de Refinacion; Cabrera, L. [INTEVEP S.A. Research and Technological Support Center of Petroleos de Venzuela, Caracas (Venezuela). Dept. de Refinacion; Gracia, W. [INTEVEP S.A. Research and Technological Support Center of Petroleos de Venzuela, Caracas (Venezuela). Dept. de Refinacion

    1997-06-01

    A model to predict the change of octane numbers expected in an FCC naphtha hydrotreating process as a function of the hydroprocessing severity (degree of sulfur removal) and the type of naphtha (expressed as the sulfur content and bromine number in the feedstock) is presented. When considering hydrotreating as an option for processing their catalytic naphthas, refiners search for the proper balance between the desired reduction of sulfur and olefins and the resulting undesired reduction of octane (RON and MON). In doing so, refiners should study the possibility of performing the hydrotreating at mild severities and/or the possibility of fractionating FCC naphthas to just treat a specific cut. This paper provides simple tools to study and analyze these study cases and to assess the sulfur-octane trade offs. (orig.)

  2. Upgrading of waste oils into transportation fuels using hydrotreating technologies

    Directory of Open Access Journals (Sweden)

    Sudipta De

    2014-12-01

    Full Text Available The generation of organic waste continues to increase, causing severe environmental pollution. Waste valorization is currently an emerging technology that can address this problem with an extra benefit of producing a range of valued products. In this contribution, we report the current developments in hydrotreating technologies for upgrading waste oil fractions into usable transportation fuels. Particular focus is given on the catalysts selection for a general hydroprocessing technique as well as the competitive role of those catalysts in hydrotreating and hydrocracking processes.

  3. Investigation and Modelling of Diesel Hydrotreating Reactions

    DEFF Research Database (Denmark)

    Boesen, Rasmus Risum

    on a commercial CoMo catalyst, and a simple kinetic model is presented. Hydrogenation of fused aromatic rings are known to be fast, and it is possible, that the reaction rates are limited by either internal or external mass transfer. An experiment conducted at industrial temperatures and pressure, using...... naphthalene as a model compound, have shown, that intra-particle diffusion resistance are likely to limit the reaction rate. In order to produce ULSD it is necessary to remove sulfur from some of the most refrac- tive sulfur compounds, such as sterically hindered dibenzothiophenes. Basic nitrogen com- pounds...... are known to inhibit certain hydrotreating reactions. Experimental results are pre- sented, showing the effect of 3 different nitrogen compounds, acridine, 1,4-dimethylcarabazole and 3-methylindole, on the hydrodesulfurization of a real feed and of a model compound, 4,6-dimethyldibenzothiophene. It is shown...

  4. Moving-Bed Process for Residue Hydrotreating Procédé à lit mobile pour l'hydrotraitement des résidus

    Directory of Open Access Journals (Sweden)

    Euzen J. P.

    2006-11-01

    Full Text Available A lot of chemical, petrochemical or refining processes require contact between three phases : a liquid feed, a gaseous reactant and a solid catalyst. Frequently, the catalyst activity is reduced by poisoning of active sites or coke deposits. This is especially the case with the processes used in heavy residual oils hydrotreating. As the catalyst life is reduced, the substitution or regeneration of the inactive catalyst is frequently necessary. Various solutions, such, as fixed beds used with swing reactors, fluidized beds, or moving beds with down flow of the catalyst and co-current or counter-current of the feed, can be proposed to perform this task with a minimum of time and production losses. A theoretical comparison between the performances of the various technologies has been made by means of a detailed simulation of the behaviour of each of these catalytic beds over a long period. Of course, in the models, some assumptions are necessary, like the ideal fluid and solids flows. Nevertheless, the problem remains complex because hydrodynamic, kinetic, catalyst deactivation, or thermal effects occur simultaneously, within the particules and/or in the bed as a whole. Various pilot plant data are of course used in order to build the kinetic part of the models. This comparison shows a marked advantage for the moving bed with counter-current flow between feed and catalyst owing to the systematic optimum use of the catalyst potential. Consequently, a series of experiments was made on various sized cold mockups designed to simulate counter-current movind beds. These experiments were necessary to demonstrate the feasability of the process, to specify the relations among gas and liquid superficial velocities, particles and fluids properties, and hydrodynamic regimes, and to develop the scale-up rules. The main goal is to secure a uniform distribution of the two fluids through out the whole bed of catalyst, and at the same time a regular progression of

  5. In-line estimation of sulfur and nitrogen contents during hydrotreating of middle distillates

    Directory of Open Access Journals (Sweden)

    M. E. Pacheco

    2009-12-01

    Full Text Available The main objective of this work is analyzing whether it is possible to develop an empirical correlation for in-line estimation of the sulfur and nitrogen contents of the middle distillates Hydrotreating (HDT products for control purposes. Correlations are based only on readily available in-line information of specific gravity variation between feedstock and products, without considering any piece of information about the kinetic behavior of the catalyst. Experimental data were obtained in pilot plants under operating conditions that are representative of refinery operations. Results indicate that the removal of nitrogen and sulfur compounds during middle distillates HDT can be monitored in-line in real time, based on the available measurements of specific gravity. This allows for development and implementation of advanced in-line procedures for monitoring and control of the HDT process in real time.

  6. Mapping reactor operating regimes for heavy gas oil hydrotreating

    Energy Technology Data Exchange (ETDEWEB)

    Munteanu, Mugurel Catalin; Chen, Jinwen [CanmetENERGY, Natural Resources Canada (Canada)

    2011-07-01

    Hydrotreating (HDT) is used in oil refineries at temperatures of 350-400 degree C and pressure of 50-100 bars in a fixed bed to improve the quality of distillate fraction. HDT operates as a gas-liquid-solid process, trickle bed. Efforts have been made to model it but volatilization of liquid oil is often ignored. The aim of this paper is to predict vapor-liquid equilibrium (VLE) for a typical heavy distillate feed in pilot plant hydrotreaters. The study was conducted under various operating conditions and a flash calculation program calibrated in-house was used to predict VLE. VLE values were found and results showed that higher pressure, lower gas/oil ratio and temperature should be used to maintain the desired operating regimes when hydrotreating heavy distillate feed. This study determined the operating conditions for maintaining the desired operating regimes and these findings could be useful for operators.

  7. Chemical kinetics and oil shale process design

    Energy Technology Data Exchange (ETDEWEB)

    Burnham, A.K.

    1993-07-01

    Oil shale processes are reviewed with the goal of showing how chemical kinetics influences the design and operation of different processes for different types of oil shale. Reaction kinetics are presented for organic pyrolysis, carbon combustion, carbonate decomposition, and sulfur and nitrogen reactions.

  8. Hydrotreating of heavy gas oil derived from Athabasca bitumen using NiMo/Al2O3 catalyst containing boron and phosphorus : effects of process conditions on the product selectivity

    Energy Technology Data Exchange (ETDEWEB)

    Ferdous, D.; Dalai, A.K. [Saskatchewan Univ., Saskatoon, SK (Canada). Dept. of Chemistry and Chemical Engineering; Adjaye, J. [Syncrude Canada Ltd., Edmonton, AB (Canada). Edmonton Research Centre

    2004-07-01

    In response to concerns regarding the depletion of conventional oil reserves, there has been much interest in modifying the hydrotreating process for upgrading tar sands and shale oils for producing transportation fuels. Oil sand bitumens and their derived products have a high level of nitrogen which deactivates the catalysts used in fluid catalytic cracking and hydrocracking. A better catalyst is needed to efficiently remove nitrogen from oil sand-derived gas oils. In this study, a trickle-bed reactor containing NiMo/Al{sub 2}O{sub 3} catalysts with boron and phosphorous was used to remove the sulfur and nitrogen from heavy gas oils derived from Athabasca bitumen. The operating conditions of the reactor in terms of temperature and pressure were described. Sulfur and nitrogen conversion was found to increase substantially with the boron catalysts. Gasoline selectivity also increased with an increase in temperature. However, a change in operating conditions did not significantly affect the net content of the gas oil fraction. This study also compared the results of using either the boron or phosphorous catalyst.

  9. Isoconversional kinetics of thermally stimulated processes

    CERN Document Server

    Vyazovkin, Sergey

    2015-01-01

    The use of isoconversional kinetic methods for analysis of thermogravimetric and calorimetric data on thermally stimulated processes is quickly growing in popularity. The purpose of this book is to create the first comprehensive resource on the theory and applications of isoconversional methodology. The book introduces the reader to the kinetics of physical and chemical condensed phase processes that occur as a result of changing temperature and discusses how isoconversional analysis can provide important kinetic insights into them. The book will help the readers to develop a better understanding of the methodology, and promote its efficient usage and successful development.

  10. Characterization of Hydrotreated Fast Pyrolysis Liquids

    NARCIS (Netherlands)

    Oasmaa, A.; Kuoppala, E.; Ardiyanti, A.; Venderbosch, R. H.; Heeres, H. J.

    This paper focuses on analytical methods to determine the composition of hydrotreated fast pyrolysis liquids. With this information, it is possible to gain insights in the chemical transformations taking place during catalytic hydrotreatment (hydrogenation and/or hydrodeoxygenation, H DO) of

  11. From biomass to fuels: Hydrotreating of oxygenated compounds

    Energy Technology Data Exchange (ETDEWEB)

    Gandarias, I.; Barrio, V.L.; Requies, J.; Arias, P.L.; Cambra, J.F.; Gueemez, M.B. [School of Engineering (UPV/EHU), c/ Alameda Urquijo s/n, 48013 Bilbao (Spain)

    2008-07-15

    Biomass is a renewable alternative to fossil raw materials in the production of liquid fuels and chemicals. Pyrolyzed biomass derived liquids contain oxygenated molecules that need to be removed to improve the stability of these liquids. A hydrotreating process, hydrodeoxygenation (HDO), is commonly used for this purpose. Thus, the aim of this work is to examine the role of advanced NiMo and NiW catalysts developed for HDS purposes in a HDO reaction. In addition, product distribution and catalyst stability are studied against changes in the feed composition, the solvent, and the catalyst pretreatment. (author)

  12. Study On Hydrotreating Of -Coker Distillate(S)

    International Nuclear Information System (INIS)

    Menoufy, M.F.; Abdel- Aleim, G.M.; Ebrahim, M.S.; Abdel-Aaty, M.

    2004-01-01

    The primary method to remove sulfur , improve cetane index and reduce aromatic content of gas oil I diesel is hydro processing. Therefore, the significant advancements in hydro treating of light coker gas oil (LCGO) derived from delayed coker unit at Suez Oil Processing Company have been performed in a cata-test fixed bed micro-reactor unit, using a commercial CoMo/ Al 2 O 3 Catalyst after sulfidation. The operating conditions were varied in order to study the impact of these processes conditions (temperature 275-400 degree C, hydrogen pressure 30-85 bar, and hourly space velocity 0.5-1.5 h -1 ) on the yield , and quality of gas oil within hydrotreating regime, which is the important to aid the optimization of the process from the environmental regulations and national market demands point of view. The present investigation is conducted on the LCGO, which was selected as a hydrotreated feedstock due to its higher unsaturated hydrocarbon contents ( aromatics and olefins) and hetero atom (sulfur and nitrogen), in order to produce an upgraded gas oil acceptable as transportation fuel according to the environmental and national regulation, and /or the world wide fuel charter december 2002

  13. Neutron inverse kinetics via Gaussian Processes

    International Nuclear Information System (INIS)

    Picca, Paolo; Furfaro, Roberto

    2012-01-01

    Highlights: ► A novel technique for the interpretation of experiments in ADS is presented. ► The technique is based on Bayesian regression, implemented via Gaussian Processes. ► GPs overcome the limits of classical methods, based on PK approximation. ► Results compares GPs and ANN performance, underlining similarities and differences. - Abstract: The paper introduces the application of Gaussian Processes (GPs) to determine the subcriticality level in accelerator-driven systems (ADSs) through the interpretation of pulsed experiment data. ADSs have peculiar kinetic properties due to their special core design. For this reason, classical – inversion techniques based on point kinetic (PK) generally fail to generate an accurate estimate of reactor subcriticality. Similarly to Artificial Neural Networks (ANNs), Gaussian Processes can be successfully trained to learn the underlying inverse neutron kinetic model and, as such, they are not limited to the model choice. Importantly, GPs are strongly rooted into the Bayes’ theorem which makes them a powerful tool for statistical inference. Here, GPs have been designed and trained on a set of kinetics models (e.g. point kinetics and multi-point kinetics) for homogeneous and heterogeneous settings. The results presented in the paper show that GPs are very efficient and accurate in predicting the reactivity for ADS-like systems. The variance computed via GPs may provide an indication on how to generate additional data as function of the desired accuracy.

  14. Kinetic study of solid-state processes

    International Nuclear Information System (INIS)

    Malek, Jiri; Mitsuhashi, Takefumi

    2003-01-01

    A simple method for kinetic analysis of solid-state processes has been developed and the criteria capable of classifying different processes are explored. They provide a useful tool for the determination of the most suitable kinetic model. The method has been applied to the analysis of calorimetric data corresponding to the crystallization processes in amorphous ZrO 2 . It is found that the crystallization kinetics of amorphous powder sample exhibits a complex behavior under non-isothermal conditions. A two-parameter model provides a satisfactory description of the crystallization process for isothermal and non-isothermal conditions. This enables better control of crystallization extent in fine ZrO 2 powders that is important for preparation of zirconia ceramics with defined properties. (author)

  15. Kinetics and thermodynamics of living copolymerization processes.

    Science.gov (United States)

    Gaspard, Pierre

    2016-11-13

    Theoretical advances are reported on the kinetics and thermodynamics of free and template-directed living copolymerizations. Until recently, the kinetic theory of these processes had only been established in the fully irreversible regime, in which the attachment rates are only considered. However, the entropy production is infinite in this regime and the approach to thermodynamic equilibrium cannot be investigated. For this purpose, the detachment rates should also be included. Inspite of this complication, the kinetics can be exactly solved in the regimes of steady growth and depolymerization. In this way, analytical expressions are obtained for the mean growth velocity, the statistical properties of the copolymer sequences, as well as the thermodynamic entropy production. The results apply to DNA replication, transcription and translation, allowing us to understand important aspects of molecular evolution.This article is part of the themed issue 'Multiscale modelling at the physics-chemistry-biology interface'. © 2016 The Author(s).

  16. Processes of aggression described by kinetic method

    Science.gov (United States)

    Aristov, V. V.; Ilyin, O.

    2014-12-01

    In the last decades many investigations have been devoted to theoretical models in new areas concerning description of different biological, sociological and historical processes. In the present paper we suggest a model of the Nazi Germany invasion of Poland, France and USSR based on the kinetic theory. We model this process with the Cauchy boundary problem for the two-element kinetic equations with spatial initial conditions. The solution of the problem is given in the form of traveling wave. The propagation velocity of a frontline depends on the quotient between initial forces concentrations. Moreover it is obtained that the general solution of the model can be expressed in terms of quadratures and elementary functions. Finally it is shown that the frontline velocities are complied with the historical data.

  17. Processes of aggression described by kinetic method

    International Nuclear Information System (INIS)

    Aristov, V. V.; Ilyin, O.

    2014-01-01

    In the last decades many investigations have been devoted to theoretical models in new areas concerning description of different biological, sociological and historical processes. In the present paper we suggest a model of the Nazi Germany invasion of Poland, France and USSR based on the kinetic theory. We model this process with the Cauchy boundary problem for the two-element kinetic equations with spatial initial conditions. The solution of the problem is given in the form of traveling wave. The propagation velocity of a frontline depends on the quotient between initial forces concentrations. Moreover it is obtained that the general solution of the model can be expressed in terms of quadratures and elementary functions. Finally it is shown that the frontline velocities are complied with the historical data

  18. Thermodynamics, kinetics and process control of nitriding

    DEFF Research Database (Denmark)

    Mittemeijer, Eric J.; Somers, Marcel A. J.

    1999-01-01

    As a prerequisite for predictability of properties obtained by a nitriding treatment of iron-based workpieces, the relation between the process parameters and the composition and structure of the surface layer produced must be known. At present (even) the description of thermodynamic equilibrium...... of pure iron-nitrogen phases has not been achieved fully. It has been shown that taking into account ordering of nitrogen in the epsilon and gamma' iron-nitride phases, leads to an improved understanding of the Fe-N phase diagram. Although thermodynamics indicate the state the system strives for......, the nitriding result is determined largely by the kinetics of the process. The nitriding kinetics have been shown to be characterised by the occurring local near-equilibria and stationary states at surfaces and interfaces, and the diffusion coefficient of nitrogen in the various phases, for which new data have...

  19. Processes of aggression described by kinetic method

    Energy Technology Data Exchange (ETDEWEB)

    Aristov, V. V.; Ilyin, O. [Dorodnicyn Computing Centre of Russian Academy of Sciences, Vavilova str. 40, Moscow, 119333 (Russian Federation)

    2014-12-09

    In the last decades many investigations have been devoted to theoretical models in new areas concerning description of different biological, sociological and historical processes. In the present paper we suggest a model of the Nazi Germany invasion of Poland, France and USSR based on the kinetic theory. We model this process with the Cauchy boundary problem for the two-element kinetic equations with spatial initial conditions. The solution of the problem is given in the form of traveling wave. The propagation velocity of a frontline depends on the quotient between initial forces concentrations. Moreover it is obtained that the general solution of the model can be expressed in terms of quadratures and elementary functions. Finally it is shown that the frontline velocities are complied with the historical data.

  20. Process Design and Economics for the Conversion of Lignocellulosic Biomass to Hydrocarbon Fuels: Fast Pyrolysis and Hydrotreating Bio-oil Pathway

    Energy Technology Data Exchange (ETDEWEB)

    Jones, Susanne [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Meyer, Pimphan [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Snowden-Swan, Lesley [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Padmaperuma, Asanga [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Tan, Eric [National Renewable Energy Lab. (NREL), Golden, CO (United States); Dutta, Abhijit [National Renewable Energy Lab. (NREL), Golden, CO (United States); Jacobson, Jacob [Idaho National Lab. (INL), Idaho Falls, ID (United States); Cafferty, Kara [Idaho National Lab. (INL), Idaho Falls, ID (United States)

    2013-11-01

    This report describes a proposed thermochemical process for converting biomass into liquid transportation fuels via fast pyrolysis followed by hydroprocessing of the condensed pyrolysis oil. As such, the analysis does not reflect the current state of commercially-available technology but includes advancements that are likely, and targeted to be achieved by 2017. The purpose of this study is to quantify the economic impact of individual conversion targets to allow a focused effort towards achieving cost reductions.

  1. Process Design and Economics for the Conversion of Lignocellulosic Biomass to Hydrocarbon Fuels: Fast Pyrolysis and Hydrotreating Bio-Oil Pathway

    Energy Technology Data Exchange (ETDEWEB)

    Jones, Susanne B. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Meyer, Pimphan A. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Snowden-Swan, Lesley J. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Padmaperuma, Asanga B. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Tan, Eric [National Renewable Energy Lab. (NREL), Golden, CO (United States); Dutta, Abhijit [National Renewable Energy Lab. (NREL), Golden, CO (United States); Jacobson, Jacob [Idaho National Lab. (INL), Idaho Falls, ID (United States); Cafferty, Kara [Idaho National Lab. (INL), Idaho Falls, ID (United States)

    2013-11-01

    This report describes a proposed thermochemical process for converting biomass into liquid transportation fuels via fast pyrolysis followed by hydroprocessing of the condensed pyrolysis oil. As such, the analysis does not reflect the current state of commercially-available technology but includes advancements that are likely, and targeted to be achieved by 2017. The purpose of this study is to quantify the economic impact of individual conversion targets to allow a focused effort towards achieving cost reductions.

  2. Catalytic hydrotreating of waste cooking oil for renewable diesel production

    Energy Technology Data Exchange (ETDEWEB)

    Bezergianni, Stella; Dimitriadis, Athanasios [Centre for Research and Technology Hellas (CERTH), Thessaloniki (Greece)

    2013-06-01

    A new technology based on catalytic hydrotreating of Waste Cooking Oil (WCO) for biodiesel production has been developed in the Centre for Research and Technology Hellas (CERTH). The main premise of this process is the conversion of the WCO fatty acids into normal- and iso-paraffins. The technology was evaluated in hydroprocessing pilot plants of CERTH where feedstock origin as well as optimal catalysts and operating parameters where identified. The fractionated diesel product, called ''white'' diesel exhibits excellent fuel properties including higher heating value (over 49 MJ/kg), negligible acidity, higher oxidation stability and higher cetane number ({proportional_to}77) than conventional biodiesel. The overall product yield is {proportional_to}92% v/v. This new suggested technology is extremely appealing as it employs existing refinery infrastructure and expertise, offers feedstock flexibility, leaves no by-product and above all is economically attractive. (orig.)

  3. Thermodynamics and kinetics of vesicles formation processes.

    Science.gov (United States)

    Guida, Vincenzo

    2010-12-15

    Vesicles are hollow aggregates, composed of bilayers of amphiphilic molecules, dispersed into and filled with a liquid solvent. These aggregates can be formed either as equilibrium or as out of equilibrium meta-stable structures and they exhibit a rich variety of different morphologies. The surprising richness of structures, the vast range of industrial applications and the presence of vesicles in a number of biological systems have attracted the interest of numerous researchers and scientists. In this article, we review both the thermodynamics and the kinetics aspects of the phenomena of formation of vesicles. We start presenting the thermodynamics of bilayer membranes formation and deformation, with the aim of deriving the conditions for the existence of equilibrium vesicles. Specifically, we use the results from continuum thermodynamics to discuss the possibility of formation of stable equilibrium vesicles, from both mixed amphiphiles and single component systems. We also link the bilayer membrane properties to the molecular structure of the starting amphiphiles. In the second part of this article, we focus on the dynamics and kinetics of vesiculation. We review the process of vesicles formation both from planar lamellar phase under shear and from isotropic micelles. In order to clarify the physical mechanisms of vesicles formation, we continuously draw a parallel between emulsification and vesiculation processes. Specifically, we compare the experimental results, the driving forces and the relative scaling laws identified for the two processes. Describing the dynamics of vesicles formation, we also discuss why non equilibrium vesicles can be formed by kinetics control and why they are meta-stable. Understanding how to control the properties, the stability and the formation process of vesicles is of fundamental importance for a vast number of industrial applications. Copyright © 2009. Published by Elsevier B.V.

  4. Hydrotreating of triglyceride containing gasoils

    Energy Technology Data Exchange (ETDEWEB)

    Krar, M.; Kasza, T.; Toth, C.; Baladincz, P.; Hancsok, J. (Univ. of Pannonia, Veszprem (Hungary)), Email: krarm@almos.uni-pannon.hu

    2009-07-01

    Because of the disadvantages of biodiesel, it is necessary to develop transformation methods, where excellent quality gas oil blending components are produced from triglycerides. An especially favourable opportunity could be the combination of the conversion of the triglycerides with a simultaneous upgrading of the gas oil stream. The main goal of our experiments was to investigate the feasibility of these two processes simultaneously in one catalytic system. In our experiments, sunflower oil (max. 25 %) gas oil blends were converted into products with gas oil boiling range. On the investigated catalyst under optimal process parameter combinations, product mixtures in the gas oil boiling point range with yield and excellent quality was produced successfully. The cetane number of the product mixtures were increased by 4-16 units, the CFPP values were increased by 5-7 deg C, when feedstock with 25 % sunflower oil content was used instead of feedstocks containing no sunflower oil. The reason is that the triglycerides were converted into normal paraffins, which are having high cetane number and poor cold-flow properties. It was concluded, that the blending of the sunflower oil into the gas oil did not reduce the HDS and HDA activity of the catalyst, however, its HDN activity significantly decreased. (orig.)

  5. Kinetics of fragmentation-annihilation processes

    OpenAIRE

    Filipe, JAN; Rodgers, GJ

    1996-01-01

    We investigate the kinetics of systems in which particles of one species undergo binary fragmentation and pair annihilation. In the latter, nonlinear process, fragments react at collision to produce an inert species, causing loss of mass. We analyze these systems in the reaction-limited regime by solving a continuous model within the mean-field approximation. The rate of fragmentation for a particle of mass x to break into fragments of masses y and x-y has the form x(lambda-1) (lambda > 0), a...

  6. Upgrading of syngas hydrotreated fractionated oxidized bio-oil to transportation grade hydrocarbons

    International Nuclear Information System (INIS)

    Luo, Yan; Hassan, El Barbary; Guda, Vamshi; Wijayapala, Rangana; Steele, Philip H.

    2016-01-01

    Highlights: • Hydrotreating of fractionated oxidized bio-oil with syngas was feasible. • Hydrocarbon properties were similar with all syngas H_2/CO molar ratios except viscosity. • Syngas with H_2/CO molar ratio of (4:6) produced the highest hydrocarbon yield. • The produced hydrocarbons were in the range of gasoline, jet fuel and diesel boiling points. - Abstract: Fast pyrolysis bio-oils have the potential to replace a part of transportation fuels obtained from fossil. Bio-oil can be successfully upgraded into stable hydrocarbons (gasoline, jet fuel and diesel) through a two-stage hydrodeoxygenation process. Consumption large amount of expensive hydrogen during this process is the major hurdle for commercialization of this technology. Applying syngas in the hydrotreating step can significantly reduce the cost of the whole process and make it competitive. In this study, four different models of syngas with different H_2 concentrations (H_2/CO molar ratios = 2:8, 4:6, 6:4 and 8:2) were used for the 1st-stage hydrotreating step of oxidized fractionated bio-oil (OFB). The 2nd-stage hydrocracking step was performed on the produced organic liquid products (OLPs) by using pure H_2 gas. The effect of syngas H_2 concentrations on the yields and properties of OLPs and the 2nd-stage hydrocarbons (HCs) was investigated. Physical and chemical properties of the 2nd-stage hydrocarbons were similar regardless syngas H_2 content, with the exception of the viscosity. Syngas with H_2/CO molar ratio of 4:6 gave significantly highest HCs yield (24.8 wt.%) based on the OFB. Simulated distillation analysis proved that all 2nd-stage hydrocarbons were mixture from a wide range boiling point fuels. These results also indicated that the successful 1st-stage syngas hydrotreating step was having the potential to produce different hydrocarbons.

  7. Characterization of catalytically hydrotreated coal liquid produced by solvolytic liquefaction in petroleum asphalt

    Energy Technology Data Exchange (ETDEWEB)

    Mochida, I.; Oishi, T.; Korai, Y.; Fujitsu, H.; Takeshita, K.

    1983-03-01

    A hydrotreated coal liquid produced by solvolytic liquefaction of a feed originally consisting of 66% petroleum asphalt and 34% coal liquid was characterized. The hydrotreatment was carried out over a Co-Mo catalyst in order to upgrade moderately and selectively the coal-derived fraction. The present process was found very effective to depolymerize rather selectively the coal-derived fraction, originally benzene insoluble, to be soluble in benzene in the dominant presence of petroleum asphalt, while 20% of the asphalt was converted to be distillable with ..cap alpha..-methylnaphthalene (the hydrotreatment solvent). Structural analyses of the fractions before and after hydrotreatment were compared to reveal what kinds of chemical reactions had taken place during hydro treatment. The major reactions of the coal derived fraction are hydrodeoxygenation and hydrodealkylation, both of which are effective for depolymerization. No significant hydrogenation on aromatic rings was observed. Hydrotreated liquid was further pyrolyzed to obtain oils and cokes of high quality. (14 refs.)

  8. A kinetic model for hydrodesulfurisation

    Energy Technology Data Exchange (ETDEWEB)

    Sau, M.; Narasimhan, C.S.L.; Verma, R.P. [Indian Oil Corporation Limited, Research and Development Centre, Faridabad (India)

    1997-07-01

    Due to stringent environmental considerations and related insistence on low sulfur fuels, hydrodesulfurisation has emerged as an important component of any refining scheme globally. The process is used ranging from Naphta/Kerosine hydrotreating to heavy oil hydrotreating. Processes such as Deep gas oil desulfurisation aiming at reduction of sulfur levels to less than 500 ppm have emerged as major players in the scenario. Hydrodesulfurisation (HDS) involves parallel desulfurisation of different organo-sulfur compounds present in the complex petroleum mixtures. In order to design, monitor, optimise and control the HDS reactor, it is necessary to have a detailed, yet simple model which follows the reaction chemistry accurately. In the present paper, a kinetic model is presented for HDS using continuum theory of lumping. The sulfur distribution in the reaction mixture is treated as continuum and parallel reaction networks are devised for kinetic modelling using continuum theory of lumping approach. The model based on the above approach follows the HDS chemistry reasonably well and hence the model parameters are almost feed invariant. Methods are also devised to incorporate heat and pressure effects into the model. The model has been validated based on commercial kero-HDS data. It is found that the model predictions agree with the experimental/commercial data. 17 refs.

  9. Characterization and utilization of hydrotreated products produced from the Whiterocks (Utah) tar sand bitumen-derived liquid

    Energy Technology Data Exchange (ETDEWEB)

    Tsai, C.H.; Longstaff, D.C.; Deo, M.D.; Hanson, F.V.; Oblad, A.G.

    1991-12-31

    The bitumen-derived liquid produced in a 4-inch diameter fluidized-bed reactor from the mined and crushed ore from the Whiterocks tar sand deposit has been hydrotreated in a fixed-bed reactor. The purpose was to determine the extent of upgrading as a function of process operating variable. A sulfided nickel-molybendum on alumina hydrodenitrogenation catalyst was used in all experiments. Moderately severe operating conditions were employed; that is, high reaction temperature (617--680 K) high reactor pressure (11.0--17.1 MPa) and low liquid feed rate (0.18--0.77 HSV); to achieve the desired reduction in heteroatom content. Detailed chemical structures of the bitumen-derived liquid feedstock and the hydrotreated total liquid products were determined by high resolution gas chromatography - mass spectrometry analyses. The compounds identified in the native bitumen included isoprenoids; bicyclic, tricycle, and tetracyclic terpenoids; steranes; hopanes; and perhydro-{beta}-carotenes. In addition, normal and branched alkanes and alkenes and partially dehydrogenated hydroaromatics were identified in the bitumen-derived liquid. The dominant pyrolysis reactions were: (1) the dealkylation of long alkyl side chains to form {alpha} - and isoolefins; and (2) the cleavage of alkyl chains linking aromatic and hydroaromatic clusters. Olefinic bonds were not observed in the hydrotreated product and monoaromatic hydrocarbons were the predominant aromatic species. The properties of the jet fuel fractions from the hydrotreated products met most of the jet fuel specifications. The cetane indices indicated these fractions would be suitable for use as diesel fuels.

  10. Characterization and utilization of hydrotreated products produced from the Whiterocks (Utah) tar sand bitumen-derived liquid

    Energy Technology Data Exchange (ETDEWEB)

    Tsai, C.H.; Longstaff, D.C.; Deo, M.D.; Hanson, F.V.; Oblad, A.G.

    1991-01-01

    The bitumen-derived liquid produced in a 4-inch diameter fluidized-bed reactor from the mined and crushed ore from the Whiterocks tar sand deposit has been hydrotreated in a fixed-bed reactor. The purpose was to determine the extent of upgrading as a function of process operating variable. A sulfided nickel-molybendum on alumina hydrodenitrogenation catalyst was used in all experiments. Moderately severe operating conditions were employed; that is, high reaction temperature (617--680 K) high reactor pressure (11.0--17.1 MPa) and low liquid feed rate (0.18--0.77 HSV); to achieve the desired reduction in heteroatom content. Detailed chemical structures of the bitumen-derived liquid feedstock and the hydrotreated total liquid products were determined by high resolution gas chromatography - mass spectrometry analyses. The compounds identified in the native bitumen included isoprenoids; bicyclic, tricycle, and tetracyclic terpenoids; steranes; hopanes; and perhydro-{beta}-carotenes. In addition, normal and branched alkanes and alkenes and partially dehydrogenated hydroaromatics were identified in the bitumen-derived liquid. The dominant pyrolysis reactions were: (1) the dealkylation of long alkyl side chains to form {alpha} - and isoolefins; and (2) the cleavage of alkyl chains linking aromatic and hydroaromatic clusters. Olefinic bonds were not observed in the hydrotreated product and monoaromatic hydrocarbons were the predominant aromatic species. The properties of the jet fuel fractions from the hydrotreated products met most of the jet fuel specifications. The cetane indices indicated these fractions would be suitable for use as diesel fuels.

  11. Hamiltonian kinetic theory of plasma ponderomotive processes

    International Nuclear Information System (INIS)

    McDonald, S.W.; Kaufman, A.N.

    1982-01-01

    The nonlinear nonresonant interaction of plasma waves and particles is formulated in Hamiltonian kinetic theory which treats the wave-action and particle distributions on an equal footing, thereby displaying reciprocity relations. In the quasistatic limit, a nonlinear wave-kinetic equation is obtained. The generality of the formalism allows for applications to arbitrary geometry, with the nonlinear effects expressed in terms of the linear susceptibility

  12. Hamiltonian kinetic theory of plasma ponderomotive processes

    International Nuclear Information System (INIS)

    McDonald, S.W.; Kaufman, A.N.

    1981-12-01

    The nonlinear nonresonant interaction of plasma waves and particles is formulated in a Hamiltonian kinetic theory which treats the wave-action and particle distributions on an equal footing, thereby displaying reciprocity relations. In the quasistatic limit, a nonlinear wave-kinetic equation is obtained. The generality of the formalism allows for applications to arbitrary geometry, with the nonlinear effects expressed in terms of the linear susceptibility

  13. Modeling of a three-phase reactor for bitumen-derived gas oil hydrotreating

    International Nuclear Information System (INIS)

    Chacon, R.; Canale, A.; Bouza, A.; Sanchez, Y.

    2012-01-01

    A three-phase reactor model for describing the hydrotreating reactions of bitumen-derived gas oil was developed. The model incorporates the mass-transfer resistance at the gas-liquid and liquid-solid interfaces and a kinetic rate expression based on a Langmuir-Hinshelwood-type model. We derived three correlations for determining the solubility of hydrogen (H 2 ), hydrogen sulfide (H 2 S) and ammonia (NH 3 ) in hydrocarbon mixtures and the calculation of the catalyst effectiveness factor was included. Experimental data taken from the literature were used to determine the kinetic parameters (stoichiometric coefficients, reaction orders, reaction rate and adsorption constants for hydrodesulfuration (HDS) and hydrodenitrogenation (HDN)) and to validate the model under various operating conditions. Finally, we studied the effect of operating conditions such as pressure, temperature, LHSV, H 2 /feed ratio and the inhibiting effect of H 2 S on HDS and NH 3 on HDN. (author)

  14. Transient processes in cell proliferation kinetics

    CERN Document Server

    Yakovlev, Andrej Yu

    1989-01-01

    A mathematician who has taken the romantic decision to devote himself to biology will doubtlessly look upon cell kinetics as the most simple and natural field of application for his knowledge and skills. Indeed, the thesaurus he is to master is not so complicated as, say, in molecular biology, the structural elements of the system, i. e. ceils, have been segregated by Nature itself, simple considerations of balance may be used for deducing basic equations, and numerous analogies in other areas of science also superficial add to one"s confidence. Generally speaking, this number of impression is correct, as evidenced by the very great theoretical studies on population kinetics, unmatched in other branches of mathematical biology. This, however, does not mean that mathematical theory of cell systems has traversed in its development a pathway free of difficulties or errors. The seeming ease of formalizing the phenomena of cell kinetics not infrequently led to the appearance of mathematical models lacking in adequ...

  15. Kinetic Modeling of Vacuum Gas Oil Hydrotreatment using a Molecular Reconstruction Approach Modélisation cinétique de l’hydrotraitement de distillats sous vide utilisant une approche de reconstruction moléculaire

    OpenAIRE

    Charon-Revellin N.; Dulot H.; López-García C.; Jose J.

    2010-01-01

    Vacuum Gas Oils (VGO) are heavy petroleum cuts (boiling points ranging from 350 to 550 ˚C) that can be transformed into valuable fuels (gasolines, diesels) by fluid catalytic cracking or hydrocracking. Prior to these conversion processes, hydrotreating is required in order to eliminate the impurities in VGOs. The hydrotreatment process enables to meet the environmental specifications (total sulfur contents) and to prevent nitrogen poisoning of conversion catalysts. In order to develop a kinet...

  16. Competition Between Hydrotreating and Polymerization Reactions During Pyrolysis Oil Hydrodeoxygenation

    NARCIS (Netherlands)

    Mercader, F. De Miguel; Koehorst, P. J. J.; Heeres, H. J.; Kersten, S. R. A.; Hogendoorn, J. A.

    2011-01-01

    Hydrodeoxygenation (HDO) of pyrolysis oil is an upgrading step that allows further coprocessing of the oil product in (laboratory-scale) standard refinery units to produce advanced biofuels. During HDO, desired hydrotreating reactions are in competition with polymerization reactions that can lead to

  17. Kinetic synergistic transitions in the Ostwald ripening processes

    Science.gov (United States)

    Sachkov, I. N.; Turygina, V. F.; Dolganov, A. N.

    2018-01-01

    There is proposed approach to mathematical description of the kinetic transitions in Ostwald ripening processes of volatile substance in nonuniformly heated porous materials. It is based upon the finite element method. There are implemented computer software. The main feature of the software is to calculate evaporation and condensation fluxes on the walls of a nonuniformly heated cylindrical capillary. Kinetic transitions are detected for three modes of volatile substances migration which are different by condensation zones location. There are controlling dimensionless parameters of the kinetic transition which are revealed during research. There is phase diagram of the Ostwald ripening process modes realization.

  18. Out-of-order event processing in kinetic data structures

    DEFF Research Database (Denmark)

    Abam, Mohammad; de Berg, Mark; Agrawal, Pankaj

    2011-01-01

    ’s for the maintenance of several fundamental structures such as kinetic sorting and kinetic tournament trees, which overcome the difficulty by employing a refined event scheduling and processing technique. We prove that the new event scheduling mechanism leads to a KDS that is correct except for finitely many short......We study the problem of designing kinetic data structures (KDS’s for short) when event times cannot be computed exactly and events may be processed in a wrong order. In traditional KDS’s this can lead to major inconsistencies from which the KDS cannot recover. We present more robust KDS...

  19. Kinetics and mechanism of synthetic CoS oxidation process

    Directory of Open Access Journals (Sweden)

    Štrbac N.

    2006-01-01

    Full Text Available The results of investigation of kinetics and mechanism for synthetic a-CoS oxidation process are presented in this paper. Based on experimental data obtained using DTA and XRD analysis and constructed PSD diagrams for Co-S-O system, mechanism of synthetic a-CoS oxidation process is suggested. Characteristic kinetic parameters were obtained for experimental isothermal investigations of desulfurization degree using Sharp method.

  20. Kinetic and radiation processes in cluster plasmas

    International Nuclear Information System (INIS)

    Smirnov, B.M.

    1996-01-01

    The analysis of processes is made for a cluster plasma which is a xenon arc plasma of a high pressure with an admixture of tungsten cluster ions. Because cluster ions emit radiation, this system is a light source which parameters are determined by various processes such as heat release and transport of charged particles in the plasma, radiative processes involving clusters, processes of cluster evaporation and attachment of atoms to it that leads to an equilibrium between clusters and vapor of their atoms, processes of cluster generation, processes of the ionization equilibrium between cluster ions and plasma electrons, transport of cluster ions in the discharge plasma in all directions. These processes govern by properties of a specific cluster plasma under consideration. (author)

  1. New Methods for Processing and Quantifying VO2 Kinetics to Steady State: VO2 Onset Kinetics

    Directory of Open Access Journals (Sweden)

    Craig R. McNulty

    2017-09-01

    Full Text Available Current methods of oxygen uptake (VO2 kinetics data handling may be too simplistic for the complex physiology involved in the underlying physiological processes. Therefore, the aim of this study was to quantify the VO2 kinetics to steady state across the full range of sub-ventilatory threshold work rates, with a particular focus on the VO2 onset kinetics. Ten healthy, moderately trained males participated in five bouts of cycling. Each bout involved 10 min at a percentage of the subject's ventilation threshold (30, 45, 60, 75, 90% from unloaded cycling. The VO2 kinetics was quantified using the conventional mono-exponential time constant (tau, τ, as well as the new methods for VO2 onset kinetics. Compared to linear modeling, non-linear modeling caused a deterioration of goodness of fit (main effect, p < 0.001 across all exercise intensities. Remainder kinetics were also improved using a modified application of the mono-exponential model (main effect, p < 0.001. Interestingly, the slope from the linear regression of the onset kinetics data is similar across all subjects and absolute exercise intensities, and thereby independent of subject fitness and τ. This could indicate that there are no functional limitations between subjects during this onset phase, with limitations occurring for the latter transition to steady state. Finally, the continuing use of mono-exponential modeling could mask important underlying physiology of more instantaneous VO2 responses to steady state. Consequently, further research should be conducted on this new approach to VO2 onset kinetics.

  2. Corrosion resistance of heat exchange equipment in hydrotreating Orenburg Condensate

    International Nuclear Information System (INIS)

    Teslya, B.M.; Burlov, V.V.; Parputs, I.V.; Parputs, T.P.

    1986-01-01

    The authors study the corrosion resistance of materials of construction and select appropriate materials for the fabrication of heat exchange equipment that will be serviceable under hydrotreating conditions. This paper discusses the Orenburg condensate hydrotreating unit which has been shut down repeatedly for repair because of corrosion damage to components of heat exchangers in the reactor section: tube bundles (08Kh18N10T steel), corrugated compensators (12Kh18N10T steel), and pins of the floating heads (37Kh13N8G8MFB steel). The authors recommend that the tube bundles and the compensators in heat exchangers in the reaction section should be fabricated of 08Kh21N6M2T or 10Kh17N13M2T steel. The pins have been replaced by new pins made of 10Kh17N13 X M2T steel, increasing the service life from 6-12 months to 2 years

  3. Upgrading of waste oils into transportation fuels using hydrotreating technologies

    OpenAIRE

    Sudipta De; Rafael Luque

    2014-01-01

    The generation of organic waste continues to increase, causing severe environmental pollution. Waste valorization is currently an emerging technology that can address this problem with an extra benefit of producing a range of valued products. In this contribution, we report the current developments in hydrotreating technologies for upgrading waste oil fractions into usable transportation fuels. Particular focus is given on the catalysts selection for a general hydroprocessing technique as wel...

  4. Catalytic hydrotreating of bio-oil derived from Chlorococcum sp.

    Science.gov (United States)

    Subagyono, R. R. D. J. N.; Marshall, M.; Jackson, W. R.; Chaffee, A. L.

    2018-04-01

    Hydrotreating of bio-oil derived from Chlorococcum sp. in the absence of NiMo/Al-SBA-15 catalysts has been investigated. The silica alumina supports decreased product yields (DCM solubles and hydrocarbon gases) due to severe coking. Incorporation of NiMo increased the product yields to up to 65 wt.% and increased the proportion of products in the kerosene boiling point range (C12-C17).The superiority of the high acidity supports persisted after incorporation of NiMo.

  5. Kinetics and modeling of anaerobic digestion process

    DEFF Research Database (Denmark)

    Gavala, Hariklia N.; Angelidaki, Irini; Ahring, Birgitte Kiær

    2003-01-01

    Anaerobic digestion modeling started in the early 1970s when the need for design and efficient operation of anaerobic systems became evident. At that time not only was the knowledge about the complex process of anaerobic digestion inadequate but also there were computational limitations. Thus...

  6. Integrated biological, chemical and physical processes kinetic ...

    African Journals Online (AJOL)

    ... for C and N removal, only gas and liquid phase processes were considered for this integrated model. ... kLA value for the aeration system, which affects the pH in the anoxic and aerobic reactors through CO2 gas exchange. ... Water SA Vol.

  7. Thermodynamics, kinetics and process control of nitriding

    DEFF Research Database (Denmark)

    Mittemeijer, Eric J.; Somers, Marcel A. J.

    1997-01-01

    As a prerequisite for the predictability of properties obtained by a nitriding treatment of iron based workpieces, the relation between the process parameters and the composition and structure of the surface layer produced must be known. At present, even the description of thermodynamic equilibrium...... of pure Fe-N phases has not been fully achieved. It is shown that taking into account the ordering of nitrogen in the epsilon and gamma' iron nitride phases leads to an improved understanding of the Fe-N phase diagram. Although consideration of thermodynamics indicates the state the system strives for...... for process control of gaseous nitriding by monitoring the partial pressure of oxygen in the furnace using a solid state electrolyte is provided. At the time the work was carried out the authors were in the Laboratory of Materials Science, Delft University of Technology, Rotterdamseweg 137, 2628 AL Delft...

  8. Spray Drying Processing: granules production and drying kinetics of droplets

    International Nuclear Information System (INIS)

    Mondragon, R.; Julia, J. E.; Barba, A.; Jarque, J. C.

    2013-01-01

    Spray drying is a unit operation very common in many industrial processes. For each particular application, the resulting granulated material must possess determined properties that depend on the conditions in which the spray drying processing has been carried out, and whose dependence must be known in order to optimize the quality of the material obtained. The large number of variables that influence on the processes of matter and energy transfer and on the formation of granular material has required a detailed analysis of the drying process. Over the years there have been many studies on the spray drying processing of all kind of materials and the influence of process variables on the drying kinetics of the granulated material properties obtained. This article lists the most important works published for both the spray drying processing and the drying of individual droplets, as well as studies aimed at modeling the drying kinetics of drops. (Author)

  9. Kinetic and thermodynamic modelling of TBP synthesis processes

    International Nuclear Information System (INIS)

    Azzouz, A.; Attou, M.

    1989-02-01

    The present paper deals with kinetic and thermodynamic modellisation of tributylphosphate (TBP) synthesis processes. Its aim consists in a purely comparative study of two different synthesis ways i.e. direct and indirect estirification of butanol. The methodology involves two steps. The first step consists in approximating curves which describe the process evolution and their dependence on the main parameters. The results gave a kinetic model of the process rate yielding in TBP. Further, on the basis of thermodynamic data concerning the various involved compounds a theoretical model was achieved. The calculations were carried out in Basic language and an interpolation mathematical method was applied to approximate the kinetic curves. The thermodynamic calculations were achieved on the basis of GIBBS' free energy using a VAX type computer and a VT240 terminal. The calculations accuracy was reasonable and within the norms. For each process, the confrontation of both models leads to an appreciable accord. In the two processes, the thermodynamic models were similar although the kinetic equations present different reaction orders. Hence the reaction orders were determined by a mathematical method which conists in searching the minimal difference between an empiric relation and a kinetic model with fixed order. This corresponds in fact in testing the model proposed at various reaction order around the suspected value. The main idea which results from such a work is that this kind of processes is well fitting with the model without taking into account the side chain reactions. The process behaviour is like that of a single reaction having a quasi linear dependence of the rate yielding and the reaction time for both processes

  10. Chemical kinetics, stochastic processes, and irreversible thermodynamics

    CERN Document Server

    Santillán, Moisés

    2014-01-01

    This book brings theories in nonlinear dynamics, stochastic processes, irreversible thermodynamics, physical chemistry, and biochemistry together in an introductory but formal and comprehensive manner.  Coupled with examples, the theories are developed stepwise, starting with the simplest concepts and building upon them into a more general framework.  Furthermore, each new mathematical derivation is immediately applied to one or more biological systems.  The last chapters focus on applying mathematical and physical techniques to study systems such as: gene regulatory networks and ion channels. The target audience of this book are mainly final year undergraduate and graduate students with a solid mathematical background (physicists, mathematicians, and engineers), as well as with basic notions of biochemistry and cellular biology.  This book can also be useful to students with a biological background who are interested in mathematical modeling, and have a working knowledge of calculus, differential equatio...

  11. Calculation the kinetics of the baking biscuit process

    Directory of Open Access Journals (Sweden)

    S. T. Antipov

    2013-01-01

    Full Text Available Based on the input values of the equivalent values of thermophysical units and the heat transfer coefficient were calculated: values that reflect the kinetics of the process of baking; values allowing to determine the relationship duration baking temperature in the baking chamber; the voltage of the active area of the hearth.

  12. Recrystallization kinetics of nanostructured copper processed by dynamic plastic deformation

    DEFF Research Database (Denmark)

    Lin, Fengxiang; Zhang, Yubin; Pantleon, Wolfgang

    2012-01-01

    The recrystallization kinetics of nanostructured copper samples processed by dynamic plastic deformation was investigated by electron backscatter diffraction. It was found that the evolution of the recrystallized volume fraction as a function of annealing time has a very low slope (n=0.37) when...

  13. A Study on the Kinetic Characteristics of Transmutation Process Reactor

    Energy Technology Data Exchange (ETDEWEB)

    Chung, Chang Hyun; You, Young Woo; Cho, Jae seon; Huh, Chang Wook; Kim, Doh Hyung [Seoul National University, Seoul (Korea, Republic of)

    1997-07-01

    The purpose of this study is to examine the transient heat transfer characteristics of liquid mental as the coolant used in accelerator-driven transmutation process reactor which is related the disposal of high-level radioactive nuclide. At current stage, the accelerator-driven transmutation process is investigated as the most appropriate method among many transmutation process methods. In this study, previous research works are investigated especially about the thermal hydraulics and kinetic behavior of coolant material including heat transfer of coolant in transmutation process reactor. A study on the heat transfer characteristics of liquid metal is performed based on the thermal hydraulic kinetic characteristics of liquid metal reactor which uses liquid metal coolant. Based on this study, the most appropriate material for the coolant of transmutation reactor will be recommended. 53 refs., 15 tabs., 33 figs. (author)

  14. Kinetic Simulations of Type II Radio Burst Emission Processes

    Science.gov (United States)

    Ganse, U.; Spanier, F. A.; Vainio, R. O.

    2011-12-01

    The fundamental emission process of Type II Radio Bursts has been under discussion for many decades. While analytic deliberations point to three wave interaction as the source for fundamental and harmonic radio emissions, sparse in-situ observational data and high computational demands for kinetic simulations have not allowed for a definite conclusion to be reached. A popular model puts the radio emission into the foreshock region of a coronal mass ejection's shock front, where shock drift acceleration can create eletrcon beam populations in the otherwise quiescent foreshock plasma. Beam-driven instabilities are then assumed to create waves, forming the starting point of three wave interaction processes. Using our kinetic particle-in-cell code, we have studied a number of emission scenarios based on electron beam populations in a CME foreshock, with focus on wave-interaction microphysics on kinetic scales. The self-consistent, fully kinetic simulations with completely physical mass-ratio show fundamental and harmonic emission of transverse electromagnetic waves and allow for detailled statistical analysis of all contributing wavemodes and their couplings.

  15. Model Feed for Hydrotreating of Fat for Biodiesel Production

    DEFF Research Database (Denmark)

    Biodiesel production by the transesterification of oils and fats with an alcohol to fatty acid alkyl esters is rapidly increasing worldwide. Plant oils are usually suited for transesterification, but feedstocks from waste products like trap greases and abattoir wastes are difficult to react due...... resulted in lower conversions and a much higher degree of hydrogenation than with the Pt catalyst. This protocol represents a facile method of studying hydrotreating of waste fats and oils for biodiesel production, which may be a viable alternative to current dominating transesterification technology. 1...

  16. Modeling of a three-phase reactor for bitumen-derived gas oil hydrotreating

    Energy Technology Data Exchange (ETDEWEB)

    Chacon, R.; Canale, A.; Bouza, A. [Departamento de Termodinamica y Fenomenos de Transporte. Universidad Simon Bolivar, Caracas (Venezuela, Bolivarian Republic of); Sanchez, Y. [Departamento de Procesos y Sistemas. Universidad Simon Bolivar (Venezuela, Bolivarian Republic of)

    2012-01-15

    A three-phase reactor model for describing the hydrotreating reactions of bitumen-derived gas oil was developed. The model incorporates the mass-transfer resistance at the gas-liquid and liquid-solid interfaces and a kinetic rate expression based on a Langmuir-Hinshelwood-type model. We derived three correlations for determining the solubility of hydrogen (H{sub 2}), hydrogen sulfide (H{sub 2}S) and ammonia (NH{sub 3}) in hydrocarbon mixtures and the calculation of the catalyst effectiveness factor was included. Experimental data taken from the literature were used to determine the kinetic parameters (stoichiometric coefficients, reaction orders, reaction rate and adsorption constants for hydrodesulfuration (HDS) and hydrodenitrogenation (HDN)) and to validate the model under various operating conditions. Finally, we studied the effect of operating conditions such as pressure, temperature, LHSV, H{sub 2}/feed ratio and the inhibiting effect of H{sub 2}S on HDS and NH{sub 3} on HDN. (author)

  17. Kinetic models for historical processes of fast invasion and aggression

    Science.gov (United States)

    Aristov, Vladimir V.; Ilyin, Oleg V.

    2015-04-01

    In the last few decades many investigations have been devoted to theoretical models in new areas concerning description of different biological, sociological, and historical processes. In the present paper we suggest a model of the Nazi Germany invasion of Poland, France, and the USSR based on kinetic theory. We simulate this process with the Cauchy boundary problem for two-element kinetic equations. The solution of the problem is given in the form of a traveling wave. The propagation velocity of a front line depends on the quotient between initial forces concentrations. Moreover it is obtained that the general solution of the model can be expressed in terms of quadratures and elementary functions. Finally it is shown that the front-line velocities agree with the historical data.

  18. Effects of catalytic hydrotreating on light cycle oil fuel quality

    International Nuclear Information System (INIS)

    Anabtawi, J.A.; Ali, S.A.

    1991-01-01

    This paper reports on a pilot plant study that was conducted to evaluate three commercial catalysts for hydrotreating of light cycle oil to reduce its aromatic content and improve the cetane index. The operating parameters were varied between 325 and 400 degrees C, 1 and 3 h - 1 , and 4 and 10 MPa at 535 L/L. The data showed that, in general, the product density and aromatic content decreased as the temperature or pressure increased or space velocity decreased. The cetane index improvement ranged from 7.3 to 10.0 for the Ni-W/Al 2 O 3 catalyst and from 6.1 to 10.1 for the Ni-Mo/Al 2 O 3 catalysts. The catalyst performance was evaluated in terms of hydrodesulfurization, hydrodenitrogenation, hydrogenation, aromatic saturation, and hydrogen consumption. This study confirms that light cycle oil can be hydrotreated to improve its cetane quality, thus increasing the extent of its blending ratio into the diesel pool

  19. Anaerobic digestion of buffalo dung: simulation of process kinetics

    International Nuclear Information System (INIS)

    Sahito, A.R.

    2015-01-01

    Assessment of kinetic of AD (Anaerobic Digestion) is a beneficial practice to forecast the performance of the process. It is helpful in the design of AD vessels, substrate feeding and digestate exit systems. The aim of this work was to assess the kinetics of anaerobically digested buffalo dung at different quantities of water added. It comprises the assessment of the specific methane production on the basis of VS (Volatile Solids) added in each reactor by using three first order models, i.e. the modified Gompertz model, the Cone model and the Exponential Curve Factor model. The analysis was tested by using the three statistical parameters, i.e. the coefficient of multiple determinations, the standard deviation of residuals and the Akaike's Information Criteria. The result reveals that the Exponential Curve Factor model was the best model that described the experimental data well. Moreover, there was not a direct or indirect relation between the kinetic coefficients of the AD process with the varying total or volatile solid content. (author)

  20. On kinetic description of electromagnetic processes in a quantum plasma

    International Nuclear Information System (INIS)

    Tyshetskiy, Yu.; Vladimirov, S. V.; Kompaneets, R.

    2011-01-01

    A nonlinear kinetic equation for nonrelativistic quantum plasma with electromagnetic interaction of particles is obtained in the Hartree's mean-field approximation. It is cast in a convenient form of Vlasov-Boltzmann-type equation with ''quantum interference integral'', which allows for relatively straightforward modification of existing classical Vlasov codes to incorporate quantum effects (quantum statistics and quantum interference of overlapping particles wave functions), without changing the bulk of the codes. Such modification (upgrade) of existing Vlasov codes may provide a direct and effective path to numerical simulations of nonlinear electrostatic and electromagnetic phenomena in quantum plasmas, especially of processes where kinetic effects are important (e.g., modulational interactions and stimulated scattering phenomena involving plasma modes at short wavelengths or high-order kinetic modes, dynamical screening and interaction of charges in quantum plasma, etc.) Moreover, numerical approaches involving such modified Vlasov codes would provide a useful basis for theoretical analyses of quantum plasmas, as quantum and classical effects can be easily separated there.

  1. A kinetic model for the burst phase of processive cellulases

    DEFF Research Database (Denmark)

    Præstgaard, Eigil; Olsen, Jens Elmerdahl; Murphy, Leigh

    2011-01-01

    . This approach generally accounts well for the initial time course (approximately 1 h) of the hydrolysis. We suggest that the models will be useful in attempts to rationalize the initial kinetics of processive cellulases, and demonstrate their application to some open questions, including the effect of repeated......Cellobiohydrolases (exocellulases) hydrolyze cellulose processively, i.e. by sequential cleaving of soluble sugars from one end of a cellulose strand. Their activity generally shows an initial burst, followed by a pronounced slowdown, even when substrate is abundant and product accumulation...... of the model, which can be solved analytically, shows that the burst and slowdown can be explained by the relative rates of the sequential reactions in the hydrolysis process and the occurrence of obstacles for the processive movement along the cellulose strand. More specifically, the maximum enzyme activity...

  2. Process Simulation for the Design and Scale Up of Heterogeneous Catalytic Process: Kinetic Modelling Issues

    Directory of Open Access Journals (Sweden)

    Antonio Tripodi

    2017-05-01

    Full Text Available Process simulation represents an important tool for plant design and optimization, either applied to well established or to newly developed processes. Suitable thermodynamic packages should be selected in order to properly describe the behavior of reactors and unit operations and to precisely define phase equilibria. Moreover, a detailed and representative kinetic scheme should be available to predict correctly the dependence of the process on its main variables. This review points out some models and methods for kinetic analysis specifically applied to the simulation of catalytic processes, as a basis for process design and optimization. Attention is paid also to microkinetic modelling and to the methods based on first principles, to elucidate mechanisms and independently calculate thermodynamic and kinetic parameters. Different case studies support the discussion. At first, we have selected two basic examples from the industrial chemistry practice, e.g., ammonia and methanol synthesis, which may be described through a relatively simple reaction pathway and the relative available kinetic scheme. Then, a more complex reaction network is deeply discussed to define the conversion of bioethanol into syngas/hydrogen or into building blocks, such as ethylene. In this case, lumped kinetic schemes completely fail the description of process behavior. Thus, in this case, more detailed—e.g., microkinetic—schemes should be available to implement into the simulator. However, the correct definition of all the kinetic data when complex microkinetic mechanisms are used, often leads to unreliable, highly correlated parameters. In such cases, greater effort to independently estimate some relevant kinetic/thermodynamic data through Density Functional Theory (DFT/ab initio methods may be helpful to improve process description.

  3. Detailed Modelling of Kinetic Biodegradation Processes in a Laboratory Mmicrocosm

    Science.gov (United States)

    Watson, I.; Oswald, S.; Banwart, S.; Mayer, U.

    2003-04-01

    Biodegradation of organic contaminants in soil and groundwater usually takes places via different redox processes happening sequentially as well as simultaneously. We used numerical modelling of a long-term lab microcosm experiment to simulate the dynamic behaviour of fermentation and respiration in the aqueous phase in contact with the sandstone material, and to develop a conceptual model describing these processes. Aqueous speciation, surface complexation, mineral dissolution and precipitation were taken into account also. Fermentation can be the first step of the degradation process producing intermediate species, which are subsequently consumed by TEAPs. Microbial growth and substrate utilisation kinetics are coupled via a formulation that also includes aqueous speciation and other geochemical reactions including surface complexation, mineral dissolution and precipitation. Competitive exclusion between TEAPs is integral to the conceptual model of the simulation, and the results indicate that exclusion is not complete, but some overlap is found between TEAPs. The model was used to test approaches like the partial equilibrium approach that currently make use of hydrogen levels to diagnose prevalent TEAPs in groundwater. The observed pattern of hydrogen and acetate concentrations were reproduced well by the simulations, and the results show the relevance of kinetics, lag times and inhibition, and especially that intermediate products play a key role.

  4. Catalytic hydrotreating of lignin with water-soluble molybdenum catalyst

    Energy Technology Data Exchange (ETDEWEB)

    Osmaa, A.; Johansson, A. (Technical Research Centre of Finland, Espoo (Finland). Lab. of Fuel and Process Technology)

    High yields (61% of the original lignin) of low molecular weight oil (84% of the oil eluted through GC) have been obtained by hydrotreating kraft pine lignin with a water-soluble molybdenum catalyst at 430[degree]C for 60 min. The main compounds in the product oil were phenols (8.7% of the original lignin), cyclohexanes (5.0%), benzenes (3.8%), naphthalenes (4.0%), and phenanthrenes (1.2%). The degree of hydrodeoxygenation was 98%. The quality (measured by GPC and GC) of the product was as good as when using more expensive solid NiMo-CR[sub 2]O[sub 3] catalysts. 30 refs., 6 tabs.

  5. Upgrading of coker distillate under variable hydrotreating operating conditions

    Directory of Open Access Journals (Sweden)

    H.A. Elsayed

    2011-06-01

    Full Text Available Studies on hydrotreating coker distillates, produced from a delayed coker unit were done using a commercially available CoMo/γ-Al2O3 catalyst, on which 0.2 wt% P2O5 was added in order to improve its characteristics. The experimental studies were conducted in a fixed-bed continuous-reactor (cata-test unit at temperatures (300–400 °C and total hydrogen pressure (40–65 bar. These conditions have affected the feedstock characteristics and great reduction of sulfur, aromatics and boiling ranges. Other improvements were obtained in diesel index (DI due to hydrogenation reaction of aromatics and desulfurization of its sulfur contents.

  6. Modeling texture kinetics during thermal processing of potato products.

    Science.gov (United States)

    Moyano, P C; Troncoso, E; Pedreschi, F

    2007-03-01

    A kinetic model based on 2 irreversible serial chemical reactions has been proposed to fit experimental data of texture changes during thermal processing of potato products. The model links dimensionless maximum force F*(MAX) with processing time. Experimental texture changes were obtained during frying of French fries and potato chips at different temperatures, while literature data for blanching/cooking of potato cubes have been considered. A satisfactory agreement between experimental and predicted values was observed, with root mean square values (RMSs) in the range of 4.7% to 16.4% for French fries and 16.7% to 29.3% for potato chips. In the case of blanching/cooking, the proposed model gave RMSs in the range of 1.2% to 17.6%, much better than the 6.2% to 44.0% obtained with the traditional 1st-order kinetics. The model is able to predict likewise the transition from softening to hardening of the tissue during frying.

  7. Investigations into the process kinetics of immobilized microorganisms

    Energy Technology Data Exchange (ETDEWEB)

    Voss, H; Geipel, F

    1987-01-01

    The authors present a population-structured process model of ethanol production by S. cerevisiae cells fixed in Ca alginate. Experiments were made in discontinuous and continuous fluidized-bed reactors. Living cells, both reproductive and non-reproductive, are distinguished from dead cells in the segregated reactor model. The rates of cell state change are described as a function of the ethanol concentration. The growth rate is described by a Monod model extended by inhibition functions and supplemented by a cell inhibition function. Product formation comprises a growth-associated component and a non-associated component resulting from the endogenous and maintenance metabolism. Further, a cell discharge rate from the gel is considered which is dependent both on growth and on the biomass concentration. The simulation of process kinetics and reactor dynamics with an optimum parameter vector shows an excellent adaptation for all experiments.

  8. Chemical kinetics, thermodynamics and the interpretation of in vivo processes - Part I

    International Nuclear Information System (INIS)

    Ferreira, R.

    1976-01-01

    A brief review of thermodynamic and kinetic concepts, the relationships between thermodynamic and kinetic information and the limitations of these concepts when confronted with the problems of biochemical processes and biological evaluation at the molecular level are presented [pt

  9. Oil removal of spent hydrotreating catalyst CoMo/Al{sub 2}O{sub 3} via a facile method with enhanced metal recovery

    Energy Technology Data Exchange (ETDEWEB)

    Yang, Yue [Institute of Nuclear and New Energy Technology, Tsinghua University, Beijing 100084 (China); Xu, Shengming, E-mail: smxu@tsinghua.edu.cn [Institute of Nuclear and New Energy Technology, Tsinghua University, Beijing 100084 (China); Beijing Key Lab of Radioactive Wastes Treatment, Tsinghua University, Beijing 100084 (China); Li, Zhen [Institute of Nuclear and New Energy Technology, Tsinghua University, Beijing 100084 (China); Wang, Jianlong [Institute of Nuclear and New Energy Technology, Tsinghua University, Beijing 100084 (China); Beijing Key Lab of Radioactive Wastes Treatment, Tsinghua University, Beijing 100084 (China); Zhao, Zhongwei [School of Metallurgy and Environment, Central South University, Changsha 410083, Hunan (China); Xu, Zhenghe, E-mail: zhenghe.xu@ualberta.ca [Institute of Nuclear and New Energy Technology, Tsinghua University, Beijing 100084 (China); Department of Chemical and Material Engineering, University of Alberta, Edmonton, Alberta T6G 1H9 (Canada)

    2016-11-15

    Highlights: • A novel approach for oil removal from spent hydrotreating catalysts has been developed. • Oil removal possibility is analyzed through surface characteristics. • Oil is successfully removed from spent catalysts via aqueous surfactant solution. • Over 98% Mo can be leached after oil removal and thermal treatment. • The proposed deoiling method helps to avoid detrimental impurity generation (CoMoO{sub 4}) and enhance metal recovery. - Abstract: Deoiling process is a key issue for recovering metal values from spent hydrotreating catalysts. The oils can be removed with organic solvents, but the industrialized application of this method is greatly hampered by the high cost and complex processes. Despite the roasting method is simple and low-cost, it generates hardest-to-recycle impurities (CoMoO{sub 4} or NiMoO{sub 4}) and enormous toxic gases. In this study, a novel and facile approach to remove oils from the spent hydrotreating catalysts is developed. Firstly, surface properties of spent catalysts are characterized to reveal the possibility of oil removal. And then, oils are removed with water solution under the conditions of 90 °C, 0.1 wt% SDS, 2.0 wt% NaOH and 10 ml/g L/S ratio for 4 h. Finally, thermal treatment and leaching tests are carried out to further explore the advantages of oil removal. The results show that no hardest-to-recycle impurity CoMoO{sub 4} is found in XPS spectra of thermally treated samples after deoiling and molybdenum is leached completely with sodium carbonate solution. It means that the proposed deoiling method can not only remove oils simply and without enormous harmful gases generating, but also avoid the generation of detrimental impurity and promote recycling of valuable metals from spent hydrotreating catalysts.

  10. Oil removal of spent hydrotreating catalyst CoMo/Al2O3 via a facile method with enhanced metal recovery.

    Science.gov (United States)

    Yang, Yue; Xu, Shengming; Li, Zhen; Wang, Jianlong; Zhao, Zhongwei; Xu, Zhenghe

    2016-11-15

    Deoiling process is a key issue for recovering metal values from spent hydrotreating catalysts. The oils can be removed with organic solvents, but the industrialized application of this method is greatly hampered by the high cost and complex processes. Despite the roasting method is simple and low-cost, it generates hardest-to-recycle impurities (CoMoO4 or NiMoO4) and enormous toxic gases. In this study, a novel and facile approach to remove oils from the spent hydrotreating catalysts is developed. Firstly, surface properties of spent catalysts are characterized to reveal the possibility of oil removal. And then, oils are removed with water solution under the conditions of 90°C, 0.1wt% SDS, 2.0wt% NaOH and 10ml/gL/S ratio for 4h. Finally, thermal treatment and leaching tests are carried out to further explore the advantages of oil removal. The results show that no hardest-to-recycle impurity CoMoO4 is found in XPS spectra of thermally treated samples after deoiling and molybdenum is leached completely with sodium carbonate solution. It means that the proposed deoiling method can not only remove oils simply and without enormous harmful gases generating, but also avoid the generation of detrimental impurity and promote recycling of valuable metals from spent hydrotreating catalysts. Copyright © 2016 Elsevier B.V. All rights reserved.

  11. Modeling physiological processes in plankton on enzyme kinetic principles

    Directory of Open Access Journals (Sweden)

    Ted Packard

    2004-04-01

    Full Text Available Many ecologically important chemical transformations in the ocean are controlled by biochemical enzyme reactions in plankton. Nitrogenase regulates the transformation of N2 to ammonium in some cyanobacteria and serves as the entryway for N2 into the ocean biosphere. Nitrate reductase controls the reduction of NO3 to NO2 and hence new production in phytoplankton. The respiratory electron transfer system in all organisms links the carbon oxidation reactions of intermediary metabolism with the reduction of oxygen in respiration. Rubisco controls the fixation of CO2 into organic matter in phytoplankton and thus is the major entry point of carbon into the oceanic biosphere. In addition to these, there are the enzymes that control CO2 production, NH4 excretion and the fluxes of phosphate. Some of these enzymes have been recognized and researched by marine scientists in the last thirty years. However, until recently the kinetic principles of enzyme control have not been exploited to formulate accurate mathematical equations of the controlling physiological expressions. Were such expressions available they would increase our power to predict the rates of chemical transformations in the extracellular environment of microbial populations whether this extracellular environment is culture media or the ocean. Here we formulate from the principles of bisubstrate enzyme kinetics, mathematical expressions for the processes of NO3 reduction, O2 consumption, N2 fixation, total nitrogen uptake.

  12. Modeling of subtle kinetic processes in plasma simulation

    International Nuclear Information System (INIS)

    Sydora, R.D.; Decyk, V.K.; Dawson, J.M.

    1988-01-01

    A new diagnostic method for plasma simulation models is presented which enables one to probe the subtle dielectric properties of the plasma medium. The procedure involves the removal of the background plasma response in order to isolate the effects of small perturbing influences which are externally added. We have found the technique accurately describes fundamental kinetic plasma behavior such as the shielding of individual test charges and currents. Wave emission studies and drag of test particles has been carried out in explicit particle algorithms as well as large time step implicit and gyrokinetic models. Accurate plasma behavior is produced and it is possible to investigate in detail, processes which can be compared with plasma kinetic theory. The technique of subtraction is not only limited to particle simulation models but also can be used in MHD or fluid models where resolution is difficult due to the intensity of the background response relative to the phenomena one is interested in measuring, such as a weakly grouwing instability or nonlinear mode coupling effect. (author)

  13. Incorporation of chemical kinetic models into process control

    International Nuclear Information System (INIS)

    Herget, C.J.; Frazer, J.W.

    1981-01-01

    An important consideration in chemical process control is to determine the precise rationing of reactant streams, particularly when a large time delay exists between the mixing of the reactants and the measurement of the product. In this paper, a method is described for incorporating chemical kinetic models into the control strategy in order to achieve optimum operating conditions. The system is first characterized by determining a reaction rate surface as a function of all input reactant concentrations over a feasible range. A nonlinear constrained optimization program is then used to determine the combination of reactants which produces the specified yield at minimum cost. This operating condition is then used to establish the nominal concentrations of the reactants. The actual operation is determined through a feedback control system employing a Smith predictor. The method is demonstrated on a laboratory bench scale enzyme reactor

  14. Kinetics of quasi-isoenergetic transition processes in biological macromolecules

    International Nuclear Information System (INIS)

    Petrov, E.G.; Teslenko, V.I.

    2010-01-01

    A master equation describing the evolution of averaged molecular state occupancies in molecular systems where alternation of molecular energy levels is caused by discrete dichotomous and trichotomous stochastic fields, is derived. This study is focused on the kinetics of quasi-isoenergetic transition processes in the presence of moderately high frequency stochastic field. A novel physical mechanism for temperature-independent transitions in flexible molecular systems is proposed. This mechanism becomes effective when the conformation transitions between quasi-isoenergetic molecular states take place. At room temperatures, stochastic broadening of molecular energy levels predominates the energy of low-frequency vibrations accompanying the transition. This leads to a cancellation of the temperature dependence in the stochastically averaged rate constants. As examples, physical interpretations of the temperature-independent onset of P2X 3 receptor desensitization in neuronal membranes, as well as degradation of PER2 protein in embrionic fibroblasts, are provided.

  15. Kinetics of a Migration-Driven Aggregation-Fragmentation Process

    Institute of Scientific and Technical Information of China (English)

    ZHUANGYou-Yi; LINZhen-Quan; KEJian-Hon~

    2003-01-01

    We propose a reversible model of the migration-driven aggregation-fragmentation process with the symmetric migration rate kernels K (k; j) = K′(k; j) =λkjv and the constant aggregation rates I1, I2 and fragmentation rates Jl, J2. Based on the mean-field theory, we investigate the evolution behavior of the aggregate size distributions in several cases with different values of index v. We find that the fragmentation reaction plays a more important role in the kinetic behaviors of the system than the aggregation and migration. When Jl = 0 and J2 = O, the aggregate size distributions αk(t) and bk(t) obey the conventional scaling law, while when Jl > 0 and J2 > O, they obey the modified scaling law with an exponential scaling function. The total mass of either species remains conserved.

  16. Kinetics of a Migration-Driven Aggregation-Fragmentation Process

    Institute of Scientific and Technical Information of China (English)

    ZHUANG You-Yi; LIN Zhen-Quan; KE Jian-Hong

    2003-01-01

    We propose a reversible model of the migration-driven aggregation-fragmentation process with the sym-metric migration rate kernels K(k;j) = K'(k;j) = λkjv and the constant aggregation rates I1, I2 and fragmentationrates J1, J2. Based on the mean-field theory, we investigate the evolution behavior of the aggregate size distributions inseveral cases with different values of index v. We find that the fragmentation reaction plays a more important role in the kinetic behaviors of the system than the aggregation and migration. When J1 = 0 and J2 = 0, the aggregate sizedistributions ak(t) and bk(t) obey the conventional scaling law, while when J1 > 0 and J2 > 0, they obey the modifiedscaling law with an exponential scaling function. The total mass of either species remains conserved.

  17. Kinetics of quasi-isoenergetic transition processes in biological macromolecules

    Energy Technology Data Exchange (ETDEWEB)

    Petrov, E.G., E-mail: epetrov@bitp.kiev.ua [Bogolyubov Institute for Theoretical Physics, National Academy of Sciences of Ukraine, Metrologichna Street, 14-b, UA-03680 Kiev (Ukraine); Teslenko, V.I. [Bogolyubov Institute for Theoretical Physics, National Academy of Sciences of Ukraine, Metrologichna Street, 14-b, UA-03680 Kiev (Ukraine)

    2010-10-05

    A master equation describing the evolution of averaged molecular state occupancies in molecular systems where alternation of molecular energy levels is caused by discrete dichotomous and trichotomous stochastic fields, is derived. This study is focused on the kinetics of quasi-isoenergetic transition processes in the presence of moderately high frequency stochastic field. A novel physical mechanism for temperature-independent transitions in flexible molecular systems is proposed. This mechanism becomes effective when the conformation transitions between quasi-isoenergetic molecular states take place. At room temperatures, stochastic broadening of molecular energy levels predominates the energy of low-frequency vibrations accompanying the transition. This leads to a cancellation of the temperature dependence in the stochastically averaged rate constants. As examples, physical interpretations of the temperature-independent onset of P2X{sub 3} receptor desensitization in neuronal membranes, as well as degradation of PER2 protein in embrionic fibroblasts, are provided.

  18. Kinetics of transformation of deformation processed gold-matrix composite

    Science.gov (United States)

    Wongpreedee, Kageeporn

    Gold matrix Ḏeformation-processed M&barbelow;etal M&barbelow;etal C&barbelow;omposites (DMMC) have been developed that have better strength and conductivity than conventional gold alloys. However, DMMC possess metastable two-phase microstructures, and their strength and conductivity decrease after prolonged exposure to elevated temperatures. The kinetics of the transformation from the metastable two-phase microstructure to the equilibrium single-phase solid solution is of interest. This document describes a study of the elevated temperature stability of Au DMMC's and the relationship between microstructure and resistivity of three compositions: Au-7 vol %Ag, Au-14 vol %Ag, and Au-vol 7%Pt. DMMC samples were prepared by a powder metallurgy technique and mechanical processes. The smallest final diameter of these wires was 120 mum. Avrami and Arrhenius relations were used to evaluate the kinetic transformation. The extensive deformation used to produce these composites reshaped the initially equi-axed powder particles into a nanofilamentary composite. Electrical resistivity measurements were used to determine the degree of transformation from the initial metastable nano-filamentary composite to the equilibrium solid solution condition. These measurements indicated that this transformation in Au-14 at%Ag, Au-7 at %Ag Au and Au-7 at %Pt DMMC wires proceeded with activation energies of 141, 156, and 167 kJ/mol, respectively. It is thought that these empirically determined activation energies differ from those determined in single crystal, planar interface Au-Ag and Au-Pt diffusion couples due to chemical potential, surface curvature, and strain effects. The DMMC systems reach the equilibrium solid solution condition faster than single crystal, planar interface systems for two reasons: (1) far more defects (dislocations, grain boundaries, vacancies from non-conservative dislocation motion, etc.) are present in the Au-Ag and Au-Pt DMMC composites, and (2) the small

  19. The Characterization of Cognitive Processes Involved in Chemical Kinetics Using a Blended Processing Framework

    Science.gov (United States)

    Bain, Kinsey; Rodriguez, Jon-Marc G.; Moon, Alena; Towns, Marcy H.

    2018-01-01

    Chemical kinetics is a highly quantitative content area that involves the use of multiple mathematical representations to model processes and is a context that is under-investigated in the literature. This qualitative study explored undergraduate student integration of chemistry and mathematics during problem solving in the context of chemical…

  20. Production of Gasoline and Diesel from Biomass via Fast Pyrolysis, Hydrotreating and Hydrocracking: A Design Case

    Energy Technology Data Exchange (ETDEWEB)

    Jones, Susanne B.; Valkenburt, Corinne; Walton, Christie W.; Elliott, Douglas C.; Holladay, Johnathan E.; Stevens, Don J.; Kinchin, Christopher; Czernik, Stefan

    2009-02-25

    The purpose of this study is to evaluate a processing pathway for converting biomass into infrastructure-compatible hydrocarbon biofuels. This design case investigates production of fast pyrolysis oil from biomass and the upgrading of that bio-oil as a means for generating infrastructure-ready renewable gasoline and diesel fuels. This study has been conducted using similar methodology and underlying basis assumptions as the previous design cases for ethanol. The overall concept and specific processing steps were selected because significant data on this approach exists in the public literature. The analysis evaluates technology that has been demonstrated at the laboratory scale or is in early stages of commercialization. The fast pyrolysis of biomass is already at an early stage of commercialization, while upgrading bio-oil to transportation fuels has only been demonstrated in the laboratory and at small engineering development scale. Advanced methods of pyrolysis, which are under development, are not evaluated in this study. These may be the subject of subsequent analysis by OBP. The plant is designed to use 2000 dry metric tons/day of hybrid poplar wood chips to produce 76 million gallons/year of gasoline and diesel. The processing steps include: 1.Feed drying and size reduction 2.Fast pyrolysis to a highly oxygenated liquid product 3.Hydrotreating of the fast pyrolysis oil to a stable hydrocarbon oil with less than 2% oxygen 4.Hydrocracking of the heavy portion of the stable hydrocarbon oil 5.Distillation of the hydrotreated and hydrocracked oil into gasoline and diesel fuel blendstocks 6. Hydrogen production to support the hydrotreater reactors. The "as received" feedstock to the pyrolysis plant will be "reactor ready". This development will likely further decrease the cost of producing the fuel. An important sensitivity is the possibility of co-locating the plant with an existing refinery. In this case, the plant consists only of the first three steps: feed

  1. Production of Gasoline and Diesel from Biomass via Fast Pyrolysis, Hydrotreating and Hydrocracking: A Design Case

    Energy Technology Data Exchange (ETDEWEB)

    Jones, Susanne B.; Valkenburt, Corinne; Walton, Christie W.; Elliott, Douglas C.; Holladay, Johnathan E.; Stevens, Don J.; Kinchin, Christopher; Czernik, Stefan

    2009-02-28

    The purpose of this study is to evaluate a processing pathway for converting biomass into infrastructure-compatible hydrocarbon biofuels. This design case investigates production of fast pyrolysis oil from biomass and the upgrading of that bio-oil as a means for generating infrastructure-ready renewable gasoline and diesel fuels. This study has been conducted using the same methodology and underlying basis assumptions as the previous design cases for ethanol. The overall concept and specific processing steps were selected because significant data on this approach exists in the public literature. The analysis evaluates technology that has been demonstrated at the laboratory scale or is in early stages of commercialization. The fast pyrolysis of biomass is already at an early stage of commercialization, while upgrading bio-oil to transportation fuels has only been demonstrated in the laboratory and at small engineering development scale. Advanced methods of pyrolysis, which are under development, are not evaluated in this study. These may be the subject of subsequent analysis by OBP. The plant is designed to use 2000 dry metric tons/day of hybrid poplar wood chips to produce 76 million gallons/year of gasoline and diesel. The processing steps include: 1.Feed drying and size reduction 2.Fast pyrolysis to a highly oxygenated liquid product 3.Hydrotreating of the fast pyrolysis oil to a stable hydrocarbon oil with less than 2% oxygen 4.Hydrocracking of the heavy portion of the stable hydrocarbon oil 5.Distillation of the hydrotreated and hydrocracked oil into gasoline and diesel fuel blendstocks 6. Hydrogen production to support the hydrotreater reactors. The “as received” feedstock to the pyrolysis plant will be “reactor ready.” This development will likely further decrease the cost of producing the fuel. An important sensitivity is the possibility of co-locating the plant with an existing refinery. In this case, the plant consists only of the first three steps

  2. Electron microscopy studies of activation mechanisms in hydrotreating catalysis

    DEFF Research Database (Denmark)

    Dahl-Petersen, Christian

    The aim of this work is to remedy the limited fundamental insight that exists in terms of the activation and formation of hydrotreating catalysts utilized in industrial oil refining of crude oil. This is done through numerous studies of the conversion of industrially relevant molybdenum oxide...... larger amount of formed MoS2. MoS2 forms in one of two conformations of the two-dimensional atomic structure that is either in an orientation parallel or perpendicular to the nanoparticle surface. Both the initial growth of MoS2 and the subsequent formation of multi-layered structures is addressed....... This shows that initial growth tends to form an apparent bond between the MoO2 surface and the MoS2 edge and that the layer size increases through coalescence. For multi-layered structures, it is found that MoS2 layers grow through a layer-under-layer mechanism, where defects in the outer layers enable...

  3. Features of hydrotreating catalytic cracking feed and heavy slow coking gas oils

    Energy Technology Data Exchange (ETDEWEB)

    Yefremov, N.I.; Kushnarev, D.F.; Frolov, P.A.; Chagovets, A.N.; Kalabin, G.A.

    1993-12-31

    A possible means of more extensive processing of crude oil is the use, in catalytic cracking, of heavy coking gas oils (HCGOs), a feature of which is a higher content of polycyclic aromatic compounds and resins by comparison with straight-run vacuum distillates. The presence of these compounds in catalytic cracking feed causes a reduction in the product yield and increased coke formation. Therefore, one of the problems of hydrotreating feedstock of this kind is the hydrogenation of polycyclic arenes. Processes of extensive desulphurization and denitration occur in parallel, since the sulphur and nitrogen compounds of HCGO are chiefly condensed benzoderivatives of thiophene, pyridine and carbazole, and largely concentrated in heavy aromatic and resinous fractions. The composition of the saturated part of the cracking feed plays a large role in achieving the optimum yields of gaseous and gasoline fractions. Thus an increase in the proportion of cyclanes in the feed raises the gasoline yield. In this way, an investigation of the hydrocarbon conversions during the hydrotreatment of cracking feed is of great importance. The present paper sets out the results for studying the change in the group-structural characteristics of the hydrogenation products of a mixture containing 30% HCGOs according to data of {sup 1}H and {sup 13}C NMR spectroscopy. 7 refs., 7 figs., 1 tab.

  4. Comparison among hydrotreating technologies to produce high quality diesel; Comparacao de tecnologias de hidrotratamento para obtencao de diesel de alta qualidade

    Energy Technology Data Exchange (ETDEWEB)

    Lima, Jorge R.D.; Rosa, Carlos A.R. da; Belato, Donizeti A.S.; Monteiro, Denise B. da R.; Monteiro, Carlos A.A.; Lima, Daniela D.S. [PETROBRAS, Rio de Janeiro, RJ (Brazil)

    2004-07-01

    The PETROBRAS Refineries, over a long time, are being adapted to be able to process crude oil from Campos Basin, which today is responsible for 70-80% of total Brazilian production. However the Campos Basin crude has very individual characteristics - when compared with the well known Arabian Light - and therefore it became necessary to acquire the knowledge of its behavior together with its refined products in traditional processes, in which we include the Hydrotreating (HDT). The main objective of this work is to analyze the HDT process schemes and its performance when operating with such a different feedstock, in order to achieve the product's quality requirements. (author)

  5. Comparison among hydrotreating technologies to produce high quality diesel; Comparacao de tecnologias de hidrotratamento para obtencao de diesel de alta qualidade

    Energy Technology Data Exchange (ETDEWEB)

    Lima, Jorge R.D.; Rosa, Carlos A.R. da; Belato, Donizeti A.S.; Monteiro, Denise B. da R.; Monteiro, Carlos A.A.; Lima, Daniela D.S. [PETROBRAS, Rio de Janeiro, RJ (Brazil)

    2004-07-01

    The PETROBRAS Refineries, over a long time, are being adapted to be able to process crude oil from Campos Basin, which today is responsible for 70-80% of total Brazilian production. However the Campos Basin crude has very individual characteristics - when compared with the well known Arabian Light - and therefore it became necessary to acquire the knowledge of its behavior together with its refined products in traditional processes, in which we include the Hydrotreating (HDT). The main objective of this work is to analyze the HDT process schemes and its performance when operating with such a different feedstock, in order to achieve the product's quality requirements. (author)

  6. Kinetic analysis of overlapping multistep thermal decomposition comprising exothermic and endothermic processes: thermolysis of ammonium dinitramide.

    Science.gov (United States)

    Muravyev, Nikita V; Koga, Nobuyoshi; Meerov, Dmitry B; Pivkina, Alla N

    2017-01-25

    This study focused on kinetic modeling of a specific type of multistep heterogeneous reaction comprising exothermic and endothermic reaction steps, as exemplified by the practical kinetic analysis of the experimental kinetic curves for the thermal decomposition of molten ammonium dinitramide (ADN). It is known that the thermal decomposition of ADN occurs as a consecutive two step mass-loss process comprising the decomposition of ADN and subsequent evaporation/decomposition of in situ generated ammonium nitrate. These reaction steps provide exothermic and endothermic contributions, respectively, to the overall thermal effect. The overall reaction process was deconvoluted into two reaction steps using simultaneously recorded thermogravimetry and differential scanning calorimetry (TG-DSC) curves by considering the different physical meanings of the kinetic data derived from TG and DSC by P value analysis. The kinetic data thus separated into exothermic and endothermic reaction steps were kinetically characterized using kinetic computation methods including isoconversional method, combined kinetic analysis, and master plot method. The overall kinetic behavior was reproduced as the sum of the kinetic equations for each reaction step considering the contributions to the rate data derived from TG and DSC. During reproduction of the kinetic behavior, the kinetic parameters and contributions of each reaction step were optimized using kinetic deconvolution analysis. As a result, the thermal decomposition of ADN was successfully modeled as partially overlapping exothermic and endothermic reaction steps. The logic of the kinetic modeling was critically examined, and the practical usefulness of phenomenological modeling for the thermal decomposition of ADN was illustrated to demonstrate the validity of the methodology and its applicability to similar complex reaction processes.

  7. HVO, hydrotreated vegetable oil. A premium renewable biofuel for diesel engines

    Energy Technology Data Exchange (ETDEWEB)

    Mikkonen, Seppo [Neste Oil, Porvoo (Finland); Honkanen, Markku; Kuronen, Markku [Neste Oil, Espoo (Finland)

    2013-06-01

    HVO is renewable paraffinic diesel fuel produced from vegetable oils or animal fats by hydrotreating and isomerization. Composition is similar to GTL. HVO is not ''biodiesel'' which is a definition reserved for FAME. HVO can be used in diesel fuel without any ''blending wall'' as well as in addition to the FAME in EN 590. As a blending component HVO enhances fuel properties thanks to its high cetane, zero aromatics and reasonable distillation range. HVO can be used for upgrading gas oils to meet diesel fuel standard and for producing premium diesel fuels. HVO is comparable to fossil diesel regarding fuel logistics, stability, water separation and microbiological growth. The use of HVO as such or in blends reduces NO{sub x} and particulate emissions. Risks for fuel system deposits and engine oil deterioration are low. Combustion is practically ash-free meaning low risk for exhaust aftertreatment life-time. Winter grade fuels down to -40 C cloud point can be produced by HVO process from many kinds of feedstocks. HVO is fully accepted by directives and fuel standards. (orig.)

  8. The unified description of kinetic and hydrodynamic processes in gases and plasmas

    International Nuclear Information System (INIS)

    Klimontovich, Yu.L.

    1992-01-01

    The unified description of kinetic and hydrodynamic processes in gases and plasmas for all values of the Knudsen number is proposed. The generalized kinetic equation consists of the additional dissipative term and is defined by the diffusion of the distribution function in the coordinate space. This equation is used for the description of nonequilibrium processes in passive and active media. (orig.)

  9. Determination of sulfur compounds in hydrotreated transformer base oil by potentiometric titration.

    Science.gov (United States)

    Chao, Qiu; Sheng, Han; Cheng, Xingguo; Ren, Tianhui

    2005-06-01

    A method was developed to analyze the distribution of sulfur compounds in model sulfur compounds by potentiometric titration, and applied to analyze hydrotreated transformer base oil. Model thioethers were oxidized to corresponding sulfoxides by tetrabutylammonium periodate and sodium metaperiodate, respectively, and the sulfoxides were titrated by perchloric acid titrant in acetic anhydride. The contents of aliphatic thioethers and total thioethers were then determined from that of sulfoxides in solution. The method was applied to determine the organic sulfur compounds in hydrotreated transformer base oil.

  10. Kinetic Analysis of the Thermal Processing of Silica and Organosilica

    NARCIS (Netherlands)

    Kappert, Emiel; Bouwmeester, Henricus J.M.; Benes, Nieck Edwin; Nijmeijer, Arian

    2014-01-01

    The incorporation of an organic group into sol–gel-derived silica causes significant changes in the structure and properties of these materials. Therefore, the thermal treatment of organosilica materials may require a different approach. In the present paper, kinetic parameters (activation energy,

  11. Kinetic models for irreversible processes on a lattice

    International Nuclear Information System (INIS)

    Wolf, N.O.

    1979-04-01

    The development and application of kinetic lattice models are considered. For the most part, the discussions are restricted to lattices in one-dimension. In Chapter 1, a brief overview of kinetic lattice model formalisms and an extensive literature survey are presented. A review of the kinetic models for non-cooperative lattice events is presented in Chapter 2. The development of cooperative lattice models and solution of the resulting kinetic equations for an infinite and a semi-infinite lattice are thoroughly discussed in Chapters 3 and 4. The cooperative models are then applied to the problem of theoretically dtermining the sticking coefficient for molecular chemisorption in Chapter 5. In Chapter 6, other possible applications of these models and several model generalizations are considered. Finally, in Chapter 7, an experimental study directed toward elucidating the mechanistic factors influencing the chemisorption of methane on single crystal tungsten is reported. In this it differs from the rest of the thesis which deals with the statistical distributions resulting from a given mechanism

  12. Kinetic models for irreversible processes on a lattice

    Energy Technology Data Exchange (ETDEWEB)

    Wolf, N.O.

    1979-04-01

    The development and application of kinetic lattice models are considered. For the most part, the discussions are restricted to lattices in one-dimension. In Chapter 1, a brief overview of kinetic lattice model formalisms and an extensive literature survey are presented. A review of the kinetic models for non-cooperative lattice events is presented in Chapter 2. The development of cooperative lattice models and solution of the resulting kinetic equations for an infinite and a semi-infinite lattice are thoroughly discussed in Chapters 3 and 4. The cooperative models are then applied to the problem of theoretically dtermining the sticking coefficient for molecular chemisorption in Chapter 5. In Chapter 6, other possible applications of these models and several model generalizations are considered. Finally, in Chapter 7, an experimental study directed toward elucidating the mechanistic factors influencing the chemisorption of methane on single crystal tungsten is reported. In this it differs from the rest of the thesis which deals with the statistical distributions resulting from a given mechanism.

  13. A new kinetic biphasic approach applied to biodiesel process intensification

    Energy Technology Data Exchange (ETDEWEB)

    Russo, V.; Tesser, R.; Di Serio, M.; Santacesaria, E. [Naples Univ. (Italy). Dept. of Chemistry

    2012-07-01

    Many different papers have been published on the kinetics of the transesterification of vegetable oil with methanol, in the presence of alkaline catalysts to produce biodiesel. All the proposed approaches are based on the assumption of a pseudo-monophasic system. The consequence of these approaches is that some experimental aspects cannot be described. For the reaction performed in batch conditions, for example, the monophasic approach is not able to reproduce the different plateau obtained by using different amount of catalyst or the induction time observed at low stirring rates. Moreover, it has been observed by operating in continuous reactors that micromixing has a dramatic effect on the reaction rate. At this purpose, we have recently observed that is possible to obtain a complete conversion to biodiesel in less than 10 seconds of reaction time. This observation is confirmed also by other authors using different types of reactors like: static mixers, micro-reactors, oscillatory flow reactors, cavitational reactors, microwave reactors or centrifugal contactors. In this work we will show that a recently proposed biphasic kinetic approach is able to describe all the aspects before mentioned that cannot be described by the monophasic kinetic model. In particular, we will show that the biphasic kinetic model can describe both the induction time observed in the batch reactors, at low stirring rate, and the very high conversions obtainable in a micro-channel reactor. The adopted biphasic kinetic model is based on a reliable reaction mechanism that will be validated by the experimental evidences reported in this work. (orig.)

  14. Heavy metal evaporation kinetics in thermal waste treatment processes

    Energy Technology Data Exchange (ETDEWEB)

    Ludwig, Ch; Stucki, S; Schuler, A J [Paul Scherrer Inst. (PSI), Villigen (Switzerland)

    1999-08-01

    To investigate the evaporation kinetics of heavy metals, experiments were performed by conventional thermogravimetry and a new method using Inductively Coupled Plasma Optical Emission Spectroscopy (ICP-OES). The new method allows online measurements in time intervals that are typically below one minute. The evaporation of Cd, Cu, Pb, and Zn from synthetic mixtures and filter ashes from municipal solid waste incineration (MSWI) was of major interest. (author) 2 figs., 4 refs.

  15. Kinetics of the nitridation of dysprosium during mechanochemical processing

    Energy Technology Data Exchange (ETDEWEB)

    Alanko, Gordon A.; Osterberg, Daniel D.; Jaques, Brian J. [Department of Materials Science and Engineering, College of Engineering, Boise State University, 1910 University Drive, Boise, ID 83725 (United States); Hurley, Michael F. [Department of Materials Science and Engineering, College of Engineering, Boise State University, 1910 University Drive, Boise, ID 83725 (United States); Center for Advanced Energy Studies, 995 University Boulevard, Idaho Falls, ID 83401 (United States); Butt, Darryl P., E-mail: darrylbutt@boisestate.edu [Department of Materials Science and Engineering, College of Engineering, Boise State University, 1910 University Drive, Boise, ID 83725 (United States); Center for Advanced Energy Studies, 995 University Boulevard, Idaho Falls, ID 83401 (United States)

    2015-01-25

    Highlights: • DyN was mechanochemically synthesized by milling pure metal under nitrogen. • Temperature and pressure were monitored to investigate reaction progress. • The effects of metal adhered to media on the impact energetics was measured. • The reactive milling kinetics are described in terms of reactive surface formation. - Abstract: Dysprosium nitride was synthesized by the reactive milling of the rare earth metal under 400 kPa nitrogen gas in a planetary ball mill. The nitrogen consumption rate was calculated from in situ temperature and pressure measurements to find the reaction extent as a function of milling time at milling speeds from 350 to 650 rpm. The results are analyzed in terms of a fundamental milling dynamics model in which the input milling energy is the primary driving force for reaction and the rate limiting step of the nitridation kinetics is the formation of chemically active surfaces. The model differs from traditional gas–solid reactions which are often limited by diffusion of a species through a surface layer or by dissociation of the gas molecule. These results give fresh insight into reactive gas–solid milling kinetics.

  16. Elementary Processes and Kinetic Modeling for Hydrogen and Helium Plasmas

    Directory of Open Access Journals (Sweden)

    Roberto Celiberto

    2017-05-01

    Full Text Available We report cross-sections and rate coefficients for excited states colliding with electrons, heavy particles and walls useful for the description of H 2 /He plasma kinetics under different conditions. In particular, the role of the rotational states in resonant vibrational excitations of the H 2 molecule by electron impact and the calculation of the related cross-sections are illustrated. The theoretical determination of the cross-section for the rovibrational energy exchange and dissociation of H 2 molecule, induced by He atom impact, by using the quasi-classical trajectory method is discussed. Recombination probabilities of H atoms on tungsten and graphite, relevant for the determination of the nascent vibrational distribution, are also presented. An example of a state-to-state plasma kinetic model for the description of shock waves operating in H 2 and He-H 2 mixtures is presented, emphasizing also the role of electronically-excited states in affecting the electron energy distribution function of free electrons. Finally, the thermodynamic properties and the electrical conductivity of non-ideal, high-density hydrogen plasma are finally discussed, in particular focusing on the pressure ionization phenomenon in high-pressure high-temperature plasmas.

  17. Diesel with low sulfur content and high cetane number produced by two stages hydrotreating procedures; Diesel com baixos teores de enxofre e alto numero de cetano a partir de hidrotratamento em dois estagios

    Energy Technology Data Exchange (ETDEWEB)

    Zotin, J L; Pacheco, M E; Souza, V P; Belato, D; Silva, R M.S. [PETROBRAS, Rio de Janeiro, RJ (Brazil). Centro de Pesquisas (CENPES)

    2004-07-01

    According to the Brazilian specifications for diesel, lower sulfur content and higher cetane number can be expected in the near future, leading to an increased capacity of hydrotreating processes. PETROBRAS has proved technology for hydrotreating processes with 8 high pressure single stage units in operation. However, the production of ultra low sulfur diesel with high cetane number may require two stages processes, with conventional hydrotreating in the first step and deep aromatic saturation (HDA), with increase in the cetane number, in the second one. In this approach, noble metal catalysts, which are more active for hydrogenation but more sensitive to sulfur and nitrogen poisoning, can be used in the second stage. In the present work, the 2 stages approach was studied for maximizing cetane number of Brazilian gasoils. The influence of operating variables and the inhibition effect by sulfur and nitrogen were analyzed. Diesel with sulfur content below 10 ppm and high aromatic conversions at relatively mild conditions were obtained with noble metal catalysts, with a cetane number increase up to 6 points in the second stage. Sulfur compounds have a stronger inhibition effect than basic nitrogen compounds on hydrogenation reaction rates, but a synergetic effect was observed when both contaminants were present in high concentrations. (author)

  18. A conservative scheme of drift kinetic electrons for gyrokinetic simulation of kinetic-MHD processes in toroidal plasmas

    Science.gov (United States)

    Bao, J.; Liu, D.; Lin, Z.

    2017-10-01

    A conservative scheme of drift kinetic electrons for gyrokinetic simulations of kinetic-magnetohydrodynamic processes in toroidal plasmas has been formulated and verified. Both vector potential and electron perturbed distribution function are decomposed into adiabatic part with analytic solution and non-adiabatic part solved numerically. The adiabatic parallel electric field is solved directly from the electron adiabatic response, resulting in a high degree of accuracy. The consistency between electrostatic potential and parallel vector potential is enforced by using the electron continuity equation. Since particles are only used to calculate the non-adiabatic response, which is used to calculate the non-adiabatic vector potential through Ohm's law, the conservative scheme minimizes the electron particle noise and mitigates the cancellation problem. Linear dispersion relations of the kinetic Alfvén wave and the collisionless tearing mode in cylindrical geometry have been verified in gyrokinetic toroidal code simulations, which show that the perpendicular grid size can be larger than the electron collisionless skin depth when the mode wavelength is longer than the electron skin depth.

  19. Emission and Performance analysis of hydrotreated refined sunflower oil as alternate fuel

    Directory of Open Access Journals (Sweden)

    J. Hemanandh

    2015-09-01

    Full Text Available The experiments were conducted by using the hydrotreated refined sunflower oil as alternative fuel in a 4-stroke, stationary DI diesel engine at a constant speed of 1500 rpm. The effects of hydrotreated vegetable oil blends on diesel engine emission and performance were studied. The emission and performance were studied for different proportions such as HTSF B25 and HTSF B100 and at different loading conditions and comparison was made with petrodiesel. The emission and performance results of HTSF B25 and HTSF B100 showed that decrease in CO by 9% and 37%, HC by 42% and 55%, NOx by 10% and 18.18%, BSFC by 25% and 12.5%. The increase in brake thermal efficiency was by 10% and 38%. It was observed from the study that hydrotreatment of refined sunflower oil could be one of the best alternative fuels for the diesel engine.

  20. Bulking sludge control. Kinetics, substrate storage, and process design aspects

    NARCIS (Netherlands)

    Martins, A.M.P.

    2004-01-01

    The activated sludge process is the preferred technology for biological wastewater treatment. Despite decades of progress and operation serious operating problems still occur with this process. One major problem is the regular occurrence of excessive growth of filamentous bacteria, phenomena known

  1. Kinetic studies on the degradation of crystal violet by the Fenton oxidation process.

    Science.gov (United States)

    Wu, H; Fan, M M; Li, C F; Peng, M; Sheng, L J; Pan, Q; Song, G W

    2010-01-01

    The degradation of dye crystal violet (CV) by Fenton oxidation process was investigated. The UV-Vis spectrogram has shown that CV can be degraded effectively by Fenton oxidation process. Different system variables namely initial H(2)O(2) concentration, initial Fe(2 + ) concentration and reaction temperature, which have effect on the degradation of CV by Fenton oxidation process, have been studied systematically. The degradation kinetics of CV was also elucidated based on the experimental data. The degradation of CV obeys the first-order reaction kinetics. The kinetic model can be described as k=1.5 exp(-(7.5)/(RT))[H(2)O(2)](0)(0.8718)[Fe(2+)](0)(0.5062). According to the IR spectrogram, it is concluded that the benzene ring of crystal violet has been destroyed by Fenton oxidation. The result will be useful in treating dyeing wastewater containing CV by Fenton oxidation process.

  2. Mechanistic, kinetic, and processing aspects of tungsten chemical mechanical polishing

    Science.gov (United States)

    Stein, David

    This dissertation presents an investigation into tungsten chemical mechanical polishing (CMP). CMP is the industrially predominant unit operation that removes excess tungsten after non-selective chemical vapor deposition (CVD) during sub-micron integrated circuit (IC) manufacture. This work explores the CMP process from process engineering and fundamental mechanistic perspectives. The process engineering study optimized an existing CMP process to address issues of polish pad and wafer carrier life. Polish rates, post-CMP metrology of patterned wafers, electrical test data, and synergy with a thermal endpoint technique were used to determine the optimal process. The oxidation rate of tungsten during CMP is significantly lower than the removal rate under identical conditions. Tungsten polished without inhibition during cathodic potentiostatic control. Hertzian indenter model calculations preclude colloids of the size used in tungsten CMP slurries from indenting the tungsten surface. AFM surface topography maps and TEM images of post-CMP tungsten do not show evidence of plow marks or intergranular fracture. Polish rate is dependent on potassium iodate concentration; process temperature is not. The colloid species significantly affects the polish rate and process temperature. Process temperature is not a predictor of polish rate. A process energy balance indicates that the process temperature is predominantly due to shaft work, and that any heat of reaction evolved during the CMP process is negligible. Friction and adhesion between alumina and tungsten were studied using modified AFM techniques. Friction was constant with potassium iodate concentration, but varied with applied pressure. This corroborates the results from the energy balance. Adhesion between the alumina and the tungsten was proportional to the potassium iodate concentration. A heuristic mechanism, which captures the relationship between polish rate, pressure, velocity, and slurry chemistry, is presented

  3. Kinetic process of mechanical alloying in Fe50Cu50

    DEFF Research Database (Denmark)

    Huang, J.Y.; Jiang, Jianzhong; Yasuda, H.

    1998-01-01

    It is shown that mechanical alloying in the immiscible Fe-Cu system is governed by the atomic shear event and shear-induced diffusion process. We found that an alpha-to-gamma phase transformation, as evidenced by the Nishiyama-Wasserman orientation relationship, occurs by simultaneous shearing...

  4. Kinetics and tissue repair process following fractional bipolar radiofrequency treatment.

    Science.gov (United States)

    Kokolakis, G; von Eichel, L; Ulrich, M; Lademann, J; Zuberbier, T; Hofmann, M A

    2018-05-15

    Fractionated radiofrequency (RF) tissue tightening is an alternative method to fractionated laser treatment of skin wrinkling, laxity and acne scars, with reduced risk of scarring or persistent pigmentation. The aim of this study was to evaluate and quantify the wound healing process after RF treatment. 12 patients were treated with a 64-pin fractional bipolar RF device with 60 mJ/pin applied energy. Confocal laser scanning microscopy (CLSM) examination was performed on day 1, day 2, day 7 and day 14 after treatment. Clinical wound healing process was measured and expressed as a percentage. All patients developed erythema, mild edema and crusts at the treated areas. Two weeks after treatment clinical symptoms resolved. During ablation patients reported moderate pain. Directly after ablation microscopic ablation zones could be detected in CLSM. Measurement of MAZ at epidermis, dermo-epidermal junction and papilary dermis showed a constant diameter until two weeks after treatment. Re-epithelization of the MAZ could be detected already 1 week after treatment. However, 2 weeks after ablation the honeycomb pattern of the epidermis was not yet completely restored. Bipolar fractionated RF treatment demonstrates clinically a rapid wound healing response. The subepidermal remodelling process still ongoing after 14 days, showing new granulation tissue. Therefore, treatment intervals of at least 14 days should be recommended to allow completion of the remodelling process.

  5. Production of fungal lipids : kinetic modeling and process design

    NARCIS (Netherlands)

    Meeuwse, P.

    2011-01-01

    Finding alternatives for fossil fuels is currently urgent. One of the new processes in this field is the production of biodiesel from lipids accumulated by microorganisms. Some yeasts and fungi accumulate lipids when a component needed for growth, usually the N-source, is limiting while the

  6. Simulation of kinetic processes in the nuclear-excited helium non-ideal dusty plasma

    International Nuclear Information System (INIS)

    Budnik, A.P.; Kosarev, V.A.; Rykov, V.A.; Fortov, V.E.; Vladimirov, V.I.; Deputatova, L.V.

    2009-01-01

    The paper is devoted to the studying of kinetic processes in the nuclear-excited plasma of the helium gas with the fine uranium (or its chemical compounds) particles admixture. A new theoretical model for the mathematical simulation of the kinetic processes in dusty plasma of helium gas was developed. The main goal of this investigation is to determine possibilities of a creation of non-ideal dusty plasma, containing nano- and micro-particles, and excited by fission fragments (copyright 2009 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

  7. A new study of the kinetics of curd production in the process of cheese manufacture.

    Science.gov (United States)

    Muñoz, Susana Vargas; Torres, Maykel González; Guerrero, Francisco Quintanilla; Talavera, Rogelio Rodríguez

    2017-11-01

    We studied the role played by temperature and rennet concentration in the coagulation process for cheese manufacture and the evaluation of their kinetics. We concluded that temperature is the main factor that determines the kinetics. The rennet concentration was unimportant probably due to the fast action of the enzyme chymosin. The Dynamic light scattering technique allowed measuring the aggregate's size and their formation kinetics. The volume fraction of solids was determined from viscosity measurements, showing profiles that are in agreement with the size profiles. The results indicate that the formation of the aggregates for rennet cheese is strongly dependent on temperature and rennet concentration. The results revealed that at 35·5 °C the volume fraction of solids has the maximum slope, indicating that at this temperature the curd is formed rapidly. The optimal temperature throughout the process was established. Second-order kinetics were obtained for the process. We observed a quadratic dependence between the rennet volume and the volume fraction of solids (curd), thereby indicating that the kinetics of the curd production should be of order two.

  8. Degradation kinetics of seven organophosphorus pesticides in milk during yoghurt processing

    Directory of Open Access Journals (Sweden)

    LI-YING BO

    2011-03-01

    Full Text Available Bovine milk spiked with seven organophosphorus pesticides, i.e., dimethoate, fenthion, malathion, methyl parathion, monocrotophos, phorate and trichlorphon, was fermented at 42 °C with commercial directed vat set (DVS starters to investigate the degradation kinetics of the pesticides during yoghurt processing. The spiked pesticides were extracted from the prepared samples with an organic solvent and analyzed by gas chromatography after purification. Based on published results that the degradation kinetics of pesticides is first order, the rate constant of degradation and the half live period of the pesticides were calculated. The results indicated that degradation of the pesticides in milk during yoghurt processing were enhanced by one or both starters, except for malathion, and the two commercial DVS starters had different influences on the degradation kinetics of the pesticides.

  9. Kinetics of Thermally Activated Physical Processes in Disordered Media

    Directory of Open Access Journals (Sweden)

    Bertrand Poumellec

    2015-07-01

    Full Text Available We describe a framework for modeling the writing and erasure of thermally-distributed activated processes that we can specifically apply to UV-induced refractive index change, particularly in fibers. From experimental measurements (isochrons and/or isotherms, this framework allows to find the distribution function of the activation energy by providing only a constant, which can be determined by a simple variable change when a few assumptions are fulfilled. From this modeling, it is possible to know the complete evolution in time of the system. It is also possible to determine the annealing conditions for extending a lifetime. This approach can also be used for other physical quantities, such as photodarkening, stress relaxation, and luminescence decay, provided that it can be described by a distribution function.

  10. Generic Schemes for Single-Molecule Kinetics. 3: Self-Consistent Pathway Solutions for Nonrenewal Processes.

    Science.gov (United States)

    Piephoff, D Evan; Cao, Jianshu

    2018-04-23

    We recently developed a pathway analysis framework (paper 1) for describing single-molecule kinetics for renewal (i.e., memoryless) processes based on the decomposition of a kinetic scheme into generic structures. In our approach, waiting time distribution functions corresponding to such structures are expressed in terms of self-consistent pathway solutions and concatenated to form measurable probability distribution functions (PDFs), affording a simple way to decompose and recombine a network. Here, we extend this framework to nonrenewal processes, which involve correlations between events, and employ it to formulate waiting time PDFs, including the first-passage time PDF, for a general kinetic network model. Our technique does not require the assumption of Poissonian kinetics, permitting a more general kinetic description than the usual rate approach, with minimal topological restrictiveness. To demonstrate the usefulness of this technique, we provide explicit calculations for our general model, which we adapt to two generic schemes for single-enzyme turnover with conformational interconversion. For each generic scheme, wherein the intermediate state(s) need not undergo Poissonian decay, the functional dependence of the mean first-passage time on the concentration of an external substrate is analyzed. When conformational detailed balance is satisfied, the enzyme turnover rate (related to the mean first-passage time) reduces to the celebrated Michaelis-Menten functional form, consistent with our previous work involving a similar scheme with all rate processes, thereby establishing further generality to this intriguing result. Our framework affords a general and intuitive approach for evaluating measurable waiting time PDFs and their moments, making it a potentially useful kinetic tool for a wide variety of single-molecule processes.

  11. KINETICS PROCESSES OF DEHYDRATION AND HEATING FISH DURING FRYING, DURING SEMI HOT AND HOT SMOKING

    Directory of Open Access Journals (Sweden)

    V. A. Pokholchenko

    2014-01-01

    Full Text Available Summary. Calculated methods of graphing of curves for kinetics of dehydration and fish heating during the processes of frying, semi hot smoking and hot smoking have been developed. The offered methods of calculating are based on the basic regularities of heat and mass exchanges of these processes. Based on the research of the regularities of dehydration on the kinetic curves, critical points were identified, that characterize the transition from the moisture removal with lower energy of its bond with material to the removal of one with higher energy bond, also the influence of the product shrinkage on the velocity of the moisture removal. These points are characteristic for the temperature curves as well. It’s suggested for the temperature curve to be replaced by broken line that consists of three straight lines that are crossing in points, corresponded with the critical moistures and critical temperatures. Significant amount of the experimental material of the research of the kinetics of dehydration and fish heating under different modes is shown by authors in the form of generalized dependencies. The method allows modeling the processes of heating and dehydrating of fish and choosing the most rational modes based on the calculated data. The proposed technique makes it possible to construct the curves of the kinetics of heating and dehydration kinetics in processes of roasting, semi hot and hot smoked fish, which allows to optimize a particular process, design more efficient in terms of consumption of raw materials and energy technology, as well as to create better machines or upgrade existing equipment into account the relationship of heat and mass transfer processes.

  12. Non-equilibrium reacting gas flows kinetic theory of transport and relaxation processes

    CERN Document Server

    Nagnibeda, Ekaterina; Nagnibeda, Ekaterina

    2009-01-01

    This volume develops the kinetic theory of transport phenomena and relaxation processes in the flows of reacting gas mixtures. The theory is applied to the modeling of non-equilibrium flows behind strong shock waves, in the boundary layer, and in nozzles.

  13. The kinetics of steam-carbon dioxide conversion, rational ways and production catalysts of process gas

    International Nuclear Information System (INIS)

    Khamroev, F.B.

    2016-01-01

    The purpose of the present work is to study the kinetics of steam-carbon dioxide conversion, rational ways and production catalysts of process gas. The experimental equation of steam-carbon methane conversion, heat stability increasing and catalyst efficiency, decreasing of hydrodynamical resistance of catalyst layer were determined.

  14. Efficient integration of stiff kinetics with phase change detection for reactive reservoir processes

    DEFF Research Database (Denmark)

    Kristensen, Morten Rode; Gerritsen, Margot G.; Thomsen, Per Grove

    2007-01-01

    We propose the use of implicit one-step Explicit Singly Diagonal Implicit Runge-Kutta (ESDIRK) methods for integration of the stiff kinetics in reactive, compositional and thermal processes that are solved using operator-splitting type approaches. To facilitate the algorithmic development we...

  15. Effect of impurities on kinetic transport processes in fusion plasmas

    Energy Technology Data Exchange (ETDEWEB)

    Braun, Stefanie

    2010-12-10

    Within the framework of this thesis, different problems arising in connection with impurities have been investigated. Collisional damping of zonal flows in tokamaks: Since the Coulomb collision frequency increases with increasing ion charge, heavy, highly charged impurities play an important role in this process. The effect of such impurities on the linear response of the plasma to an external potential perturbation, as caused by zonal flows, is calculated with analytical methods. In comparison with a pure plasma, the damping of the flows occurs, as expected, considerably faster; for experimentally relevant parameters, the enhancement exceeds the effective charge Z{sub eff} of the plasma. Impurity transport driven by microturbulence in tokamaks: With regard to impurities, it is especially important whether the resulting flows are directed inwards or outwards, since they are deleterious for core energy confinement on the one hand, but on the other hand help protecting plasma-facing components from too high energy fluxes in the edge region. A semi-analytical model is presented describing the resulting impurity fluxes and the stability boundary of the underlying mode. The main goal is to bridge the gap between, on the one hand, costly numerical simulations, which are applicable to a broad range of problems but yield scarcely traceable results, and, on the other hand, analytical theory, which might ease the interpretation of the results but is so far rather rudimentary. The model is based on analytical formulae whenever possible but resorts to a numerical treatment when the approximations necessary for an analytical solution would lead to a substantial distortion of the results. Both the direction of the impurity flux and the stability boundary are found to depend sensitively on the plasma parameters such as the impurity density and the temperature gradient. Pfirsch-Schlueter transport in stellarators: Due to geometry effects, collisional transport plays a much more

  16. Kinetics of pulp mill effluent treatment by ozone-based processes

    International Nuclear Information System (INIS)

    Ko, Chun-Han; Hsieh, Po-Hung; Chang, Meng-Wen; Chern, Jia-Ming; Chiang, Shih-Min; Tzeng, Chewn-Jeng

    2009-01-01

    The wastewaters generated from wood pulping and paper production processes are traditionally treated by biological and physicochemical processes. In order to reduce chemical oxygen demand (COD) and color to meet increasingly strict discharge standards, advanced oxidation processes (AOPs) are being adapted as polishing treatment units. Various ozone-based processes were used in this study to treat simulated wastewaters prepared from black liquor from a hardwood Kraft pulp mill in Taiwan. The experimental results showed that the COD and color were primarily removed by direct ozone oxidation and activated carbon adsorption. While the addition of activated carbon could enhance the COD and color removal during ozonation, the addition of hydrogen peroxide improved the color removal only. For the various ozone-based treatment processes, kinetic models were developed to satisfactorily predict the COD and color removal rates. According to the kinetic parameters obtained from the various ozone-based processes, the enhanced COD and color removal of ozonation in the presence of activated carbon was attributed to the regeneration of the activated carbon by ozonation. These kinetic models can be used for reactor design and process design to treat pulping wastewater using ozone-based processes.

  17. Kinetics parameters of a slurry remediation process in rotating drum bioreactors

    International Nuclear Information System (INIS)

    Esquivel-Rios, I.; Rodriguez-Meza, M. A.; Barrera-Cortes, J.

    2009-01-01

    The knowledge of biotransformation pollution dynamics in any systems is important for design and optimization purposes of biochemical processes involved. this is focus to the determination of kinetics parameters such as the maximum specific growth rate (μMAX), saturation constant (Ks), biomass yield (YX/S; X: biomass, S: substrate) and oxygen consumption (YO 2 /S; O 2 : oxygen). Several approximations, based on Monod equation, have been developed for estimating kinetics parameters in terms of concentration and type of substrate, bioprocess type and microflora available. (Author)

  18. Development of a Procedure to Apply Detailed Chemical Kinetic Mechanisms to CFD Simulations as Post Processing

    DEFF Research Database (Denmark)

    Skjøth-Rasmussen, Martin Skov; Glarborg, Peter; Jensen, Anker

    2003-01-01

    mechanism. It involves post-processing of data extracted from computational fluid dynamics simulations. Application of this approach successfully describes combustion chemistry in a standard swirl burner, the so-called Harwell furnace. Nevertheless, it needs validation against more complex combustion models......It is desired to make detailed chemical kinetic mechanisms applicable to the complex geometries of practical combustion devices simulated with computational fluid dynamics tools. This work presents a novel general approach to combining computational fluid dynamics and a detailed chemical kinetic...

  19. Simulation of the organic-waste processing in plasma with allowance for kinetics of thermochemical transformations

    Science.gov (United States)

    Messerle, V. E.; Ustimenko, A. B.

    2017-07-01

    Kinetic calculations of the plasma processing/utilization process of organic waste in air and steam ambient were carried out. It is shown that, during the time of waste residence in the plasma reactor, 0.7 and 1.2 s, at the exit from the reactor there forms a high-calorific fuel gas with a combustion heat of 3540 and 5070 kcal/kg, respectively. In this process, 1 kg of waste yields 1.16 kg of fuel gas at air gasification of waste and 0.87 kg of pure synthesis gas at steam gasification. The energy efficiency of the waste gasification process, defined by the ratio between the calorific value of the resultant fuel gas and the initial calorific value of the waste amounts to 91 % in air plasma and 98 % in steam plasma. A comparison between the results of kinetic and thermodynamic calculations has revealed their good agreement.

  20. Field-to-Fuel Performance Testing of Lignocellulosic Feedstocks: An Integrated Study of the Fast Pyrolysis/Hydrotreating Pathway

    Energy Technology Data Exchange (ETDEWEB)

    Howe, Daniel T.; Westover, Tyler; Carpenter, Daniel; Santosa, Daniel M.; Emerson, Rachel; Deutch, Steve; Starace, Anne; Kutnyakov, Igor V.; Lukins, Craig D.

    2015-05-21

    Feedstock composition can affect final fuel yields and quality for the fast pyrolysis and hydrotreatment upgrading pathway. However, previous studies have focused on individual unit operations rather than the integrated system. In this study, a suite of six pure lignocellulosic feedstocks (clean pine, whole pine, tulip poplar, hybrid poplar, switchgrass, and corn stover) and two blends (equal weight percentages whole pine/tulip poplar/switchgrass and whole pine/clean pine/hybrid poplar) were prepared and characterized at Idaho National Laboratory. These blends then underwent fast pyrolysis at the National Renewable Energy Laboratory and hydrotreatment at Pacific Northwest National Laboratory. Although some feedstocks showed a high fast pyrolysis bio-oil yield such as tulip poplar at 57%, high yields in the hydrotreater were not always observed. Results showed overall fuel yields of 15% (switchgrass), 18% (corn stover), 23% (tulip poplar, Blend 1, Blend 2), 24% (whole pine, hybrid poplar) and 27% (clean pine). Simulated distillation of the upgraded oils indicated that the gasoline fraction varied from 39% (clean pine) to 51% (corn stover), while the diesel fraction ranged from 40% (corn stover) to 46% (tulip poplar). Little variation was seen in the jet fuel fraction at 11 to 12%. Hydrogen consumption during hydrotreating, a major factor in the economic feasibility of the integrated process, ranged from 0.051 g/g dry feed (tulip poplar) to 0.070 g/g dry feed (clean pine).

  1. Process kinetics and digestion efficiency of anaerobic batch fermentation of brewer`s spent grains (BSG)

    Energy Technology Data Exchange (ETDEWEB)

    Ezeonu, F.C.; Okaka, A.N.C. [Nnamdi Azikiwe University, Awka (Nigeria). Dept. of Applied Biochemistry

    1996-12-31

    The process kinetics of optimized anaerobic batch digestion of brewer`s spent grains (BSG) reveal that biomethanation is essentially a first order reaction interrupted intermittently by mixed order reactions. An apparent cellulose degradation efficiency of approximately 60% and a lignin degradation efficiency of about 40% was observed in the optimized process. Using the Ken and Hashimoto model, the operational efficiency of the digester was determined to be 26%. (author)

  2. Photo-assisted Fenton type processes for the degradation of phenol: A kinetic study

    International Nuclear Information System (INIS)

    Kusic, Hrvoje; Koprivanac, Natalija; Bozic, Ana Loncaric; Selanec, Iva

    2006-01-01

    In this study the application of advanced oxidation processes (AOPs), dark Fenton and photo-assisted Fenton type processes; Fe 2+ /H 2 O 2 , Fe 3+ /H 2 O 2 , Fe 0 /H 2 O 2 , UV/Fe 2+ /H 2 O 2 , UV/Fe 3+ /H 2 O 2 and UV/Fe 0 /H 2 O 2 , for degradation of phenol as a model organic pollutant in the wastewater was investigated. A detail kinetic modeling which describes the degradation of phenol was performed. Mathematical models which predict phenol decomposition and formation of primary oxidation by-products: catechol, hydroquinone and benzoquinone, by applied processes were developed. The study also consist the modeling of mineralization kinetic of the phenol solution by applied AOPs. This part, besides well known reactions of Fenton and photo-Fenton chemistry, involves additional reactions which describe removal of iron from catalytic cycle through formation of ferric complexes and its regeneration induced by UV radiation. Phenol decomposition kinetic was monitored by HPLC analysis and total organic carbon content measurements (TOC). Complete phenol removal was obtained by all applied processes. Residual TOC by applied Fenton type processes ranged between 60.2 and 44.7%, while the efficiency of those processes was significantly enhanced in the presence of UV light, where residual TOC ranged between 15.2 and 2.4%

  3. Optimization and kinetic modeling of cadmium desorption from citrus peels: A process for biosorbent regeneration

    International Nuclear Information System (INIS)

    Njikam, Eloh; Schiewer, Silke

    2012-01-01

    Graphical abstract: Cadmium was completely and quickly desorbed from grapefruit peels using 0.01 M HNO 3 . The kinetics followed a novel 1st or 2nd order kinetic model, related to the remaining metal bound as the rate-determining reactant concentration. For 0.001 M HNO 3 , desorption was incomplete and the model fit less perfect. Highlights: ► Metal desorption was over 90% complete within 50 min for most desorbents. ► Models for biosorbent desorption kinetics were developed. ► Desorption kinetics best fit a novel first-order model related to remaining metal bound. ► Cd uptake after desorption by HNO 3 was similar to the original uptake. ► The optimal desorbent was 0.1 or 0.01 M acid, being fast, efficient and cheap. - Abstract: Citrus peel biosorbents are efficient in removing heavy metals from wastewater. Heavy metal recovery and sorbent regeneration are important for the financial competitiveness of biosorption with other processes. The desorbing agents HNO 3 , NaNO 3 , Ca(NO 3 ) 2 , EDTA, S, S-EDDS, and Na-Citrate were studied at different concentrations to optimize cadmium elution from orange or grapefruit peels. In most cases, desorption was fast, being over 90% complete within 50 min. However sodium nitrate and 0.001 M nitric acid were less efficient. Several new models for desorption kinetics were developed. While zero-, first- and second-order kinetics are commonly applied for modeling adsorption kinetics, the present study adapts these models to describe desorption kinetics. The proposed models relate to the number of metal-filled binding sites as the rate-determining reactant concentration. A model based on first order kinetics with respect to the remaining metal bound performed best. Cd bound in subsequent adsorption after desorption was similar to the original amount bound for desorption by nitric acid, but considerably lower for calcium nitrate as the desorbent. While complexing agents were effective desorbents, their cost is higher than that

  4. Dose dependent oxidation kinetics of lipids in fish during irradiation processing

    International Nuclear Information System (INIS)

    Tukenmez, I.; Ersen, M.S.; Bakioglu, A.T.; Bicer, A.; Pamuk, V.

    1997-01-01

    Kinetic aspects of the development of lipid oxidation in complex foods as fish in the course of irradiation were analyzed with respect to the associated formation of malonaldehyde (MA) through the reactions modified so as to be consistent with those in complex foods as fish. Air-packed anchovy (Engraulis encrasicholus) samples in polyethylene pouches were irradiated at the doses of 1, 2, 5, 10, 15,20 and 25 kGy at 20 o C in a Cs-137 gamma irradiator of 1.806 kGy/h dose rate. Immediately after each irradiation, MA contents of irradiated and unirradiated samples were determined by thiobarbituric acid test. Based on the MA formation, a kinetic model to simulate the apparent oxidation of lipid in fish as a function of irradiation dose was derived from the rate equations consistent with modified reactions. Kinetic parameters and simulation were related to conditions of lipid oxidation, and associated rancidity state of fish with respect to the doses applied in different irradiation-preservation processes. Numerical values of kinetic parameters based on the MA formation were found as a threshold dose of 0.375 kGy, an apparent yield of 1.871 μmol/kg kGy, and a maximum attainable concentration of 15.853 μmol/kg which may be used for process control and dosimetry. (author)

  5. Mechanistic and kinetic aspects of microbial inactivation in food irradiation processes

    International Nuclear Information System (INIS)

    Tukenmez, I.

    2004-01-01

    Full text: A proper reaction mechanism was searched by analyzing the inactivation processes of microorganisms during food irradiation by ionizing radiation. By employing transition-state theory, it was assumed that the overall inactivation process involves a reversible sub-lethal stress and repair reactions to form reversibly injured cell or sensitized cell, which then undergoes irreversible injury leading to dead cell. A shoulder in low dose range in survival kinetics was associated with the repair process. Depending on the postulated mechanism, kinetic model equations were derived. The kinetics of cell inactivation by irradiation was expressed as depending on irradiation dose. By using experimental data in the developed model the inactivation parameters including threshold dose, radiation yield, decimal reduction dose and minimum sterilization dose were evaluated and microbial inactivation by irradiation was simulated by using the numerical values of the parameters. Developed model and model parameters may be used for the process control and the assessment of product quality in radiation preservation of food

  6. Prediction of vapour-liquid equilibria for the kinetic study of processes based on synthesis gas

    Energy Technology Data Exchange (ETDEWEB)

    Di Serio, M.; Tesser, R.; Cozzolino, M.; Santacesaria, E. [Naples Univ., Napoli (Italy). Dept. of Chemistry

    2006-07-01

    Syngas is normally used in the production of a broad range of chemicals and fuels. In many of these processes multiphase reactors, gas-liquid or gas-liquid-solid are used. Kinetic studies in multiphase systems are often complicated by the non-ideal behaviour of reagents and/or products that are consistently partitioned between the liquid and the vapour phase. Moreover, as often kinetic data are collected in batch conditions for the liquid phase, activity coefficients of the partitioned components can consistently change during the time as a consequence of changing the composition of the reaction mixture. Therefore, it is necessary, in these cases, to known the vapor-liquid equilibria (VLE) in order to collect and to interpret correctly the kinetic data. The description of phase equilibria, at high pressures, is usually performed by means of an EOS (Equation of State) allowing the calculation of fugacity coefficients, for each component, in both phases and determining the partition coefficients but the EOS approach involves the experimental determination of the interaction parameters for all the possible binary system of the mixture. For multicomponent mixtures a complete experimental determination of vapourliquid equilibria is very hard, also considering the high pressure and temperatures used. Some predictive group contribution methods have been recently developed. In this paper, we will describe in detail the application of these methods to the methanol homologation, as an example, with the scope of determining more reliable kinetic parameters for this reaction. (orig.)

  7. Recent developments in thermoluminescence kinetics: applications to other thermally stimulated processes

    International Nuclear Information System (INIS)

    Levy, P.W.

    1985-01-01

    Recent thermoluminescence (TL) studies indicate that many kinetic properties are not in accord with the well known 1st and 2nd order TL kinetic equations. For example, the usual equations do not describe: (1) the shape of certain single glow peaks. (2) The shape of glow peaks in many glow curves containing more than one glow peak. (3) The dependence of the peak temperature, the FWHM, the shape, and other properties on the pre-measurement dose. However, the properties of some single glow peaks are precisely described, or closely approximated by, the more general basic equation from which the usual 1st and 2nd order equations are obtained as special cases. Furthermore, glow curves containing more than one glow peak are described by a system of equations that includes interactions between different types of traps and is a straightforward extension of the general one peak equation. This system - called Interactive Kinetics - accounts for most properties, and explains many anomalies, associated with glow curves containing more than one glow peak. It is particularly convenient for computerized analysis procedures. Lastly, it is suggested that other thermally stimulated processes depend on analogous interactions and are describable by similar sets of kinetic equations that are convenient for computer analysis. 11 refs., 2 figs

  8. Butia Yatay coconut oil: Process development for biodiesel production and kinetics of esterification with ethanol

    International Nuclear Information System (INIS)

    Zanuttini, M.S.; Pisarello, M.L.; Querini, C.A.

    2014-01-01

    Highlights: • Coconut oil contains high levels of phosphorous and free fatty acids. • Especial degumming process is needed in order to decrease the phosphorous content. • Kinetic constant for esterification reaction decreases as a function of time. • Two-step esterification is more efficient to reduce acidity than one-step. • Approximately 15% of esters are formed by acid-catalyzed transesterification. - Abstract: The aim of this work is to study biodiesel production using Butia Yatay coconut oil. This oil has acid values between 109 and 140 mg KOH/g, and phosphorus content in the order of 600 ppm. A three-step degumming pre-treatment of the raw material was adjusted in order to decrease the phosphorus content to approximately 200 ppm. Afterwards, a two-step esterification followed by transesterification was required in order to obtain a high-quality product. The esterification kinetics was studied including the simultaneous reactions that take place during the esterification of free fatty acids: autocatalysis, triacylglycerides hydrolysis, transesterification, and the reaction of sulphuric acid with the alcohol, being the most important ones. The kinetic parameters for the esterification and autocatalysis reactions were also obtained, being different compared to sunflower oil, due to the presence of short chain fatty acids. The kinetic constant for the esterification reaction rapidly decreases as a function of time, due to the consumption of the catalyst by the alkyl-sulphate formation reaction

  9. Flame spray synthesis of CoMo/Al2O3 hydrotreating catalysts

    DEFF Research Database (Denmark)

    Høj, Martin; Linde, Kasper; Hansen, Thomas Klint

    2011-01-01

    containing 16wt.% Mo (atomic ratio Co/Mo=1/3), which did not contain crystalline MoO3 and only small amounts of CoAl2O4. The hydrotreating activity was approximately 75% of that of commercial cobalt molybdenum catalysts prepared by wet impregnation of pre-shaped alumina extrudates. Since the commercial...... obtained consisted mostly of γ-Al2O3 with some CoAl2O4, as evidenced by X-ray diffraction (XRD) and UV–vis spectroscopy. Bulk MoO3 was not detected by XRD, except at the highest molybdenum content (32wt.%) and in the unsupported sample, indicating that molybdenum is well dispersed on the surface.......After activation by sulfidation the activity of the catalysts were measured for the three hydrotreating reactions hydrodesulfurization, hydrodenitrogenation and hydrogenation using a model oil containing dibenzothiophene, indole and naphthalene in n-heptane solution. The best catalyst was the FSP-produced material...

  10. Quantitative Surface Analysis by Xps (X-Ray Photoelectron Spectroscopy: Application to Hydrotreating Catalysts

    Directory of Open Access Journals (Sweden)

    Beccat P.

    1999-07-01

    Full Text Available XPS is an ideal technique to provide the chemical composition of the extreme surface of solid materials, vastly applied to the study of catalysts. In this article, we will show that a quantitative approach, based upon fundamental expression of the XPS signal, has enabled us to obtain a consistent set of response factors for the elements of the periodic table. In-depth spadework has been necessary to know precisely the transmission function of the spectrometer used at IFP. The set of response factors obtained enables to perform, on a routine basis, a quantitative analysis with approximately 20% relative accuracy, which is quite acceptable for an analysis of such a nature. While using this quantitative approach, we have developed an analytical method specific to hydrotreating catalysts that allows obtaining the sulphiding degree of molybdenum quite reliably and reproducibly. The usage of this method is illustrated by two examples for which XPS spectroscopy has provided with information sufficiently accurate and quantitative to help understand the reactivity differences between certain MoS2/Al2O3 or NiMoS/Al2O3-type hydrotreating catalysts.

  11. A New Approach to Deep Desulfurization of Light Cycle Oil over Ni2P Catalysts: Combined Selective Oxidation and Hydrotreating

    Directory of Open Access Journals (Sweden)

    Gwang-Nam Yun

    2018-03-01

    Full Text Available Amphiphilic phosphotungstic acid (A-PTA and Ni2P/SBA-15 catalysts were prepared to apply for selective oxidation of refractory sulfur compounds in light cycle oils and hydrotreating of the oxidized S compounds, respectively. Physical properties of the catalyst samples were analyzed by BET, CO uptake chemisorption, and TEM. Structural properties for the supported Ni2P catalysts were analyzed by X-ray diffraction (XRD and extended X-ray absorption fine structure (XAFS spectroscopy. The selective oxidation of S compounds in the LCO feed was conducted in a batch reactor at H2O2/S ratio of 10, atmospheric pressure and 353 K and then the products were fed to a continuous flow fixed-bed reactor for hydrotreating at 623 K, 3.0 MPa, and LHSV’s of 0.5–2.0 h−1. A-PTA catalyst showed a high oxidation conversion of 95% for a real LCO feed. The following hydrotreating led to a hydrodesulfurization (HDS conversion of 99.6% and a hydrodenitrogenation (HDN conversion of 94.7% over Ni2P/SBA-15, which were much higher than those of direct hydrotreating results which gave an HDS conversion of 63.5% and an HDN conversion of 17.5% based on the same LHSV of 2.0 h−1. It was revealed that the reduction in refractory nitrogen compounds after oxidative treatment contributed to the increase of the following HDS activity.

  12. Kinetic Modeling of a Silicon Refining Process in a Moist Hydrogen Atmosphere

    Science.gov (United States)

    Chen, Zhiyuan; Morita, Kazuki

    2018-06-01

    We developed a kinetic model that considers both silicon loss and boron removal in a metallurgical grade silicon refining process. This model was based on the hypotheses of reversible reactions. The reaction rate coefficient kept the same form but error of terminal boron concentration could be introduced when relating irreversible reactions. Experimental data from published studies were used to develop a model that fit the existing data. At 1500 °C, our kinetic analysis suggested that refining silicon in a moist hydrogen atmosphere generates several primary volatile species, including SiO, SiH, HBO, and HBO2. Using the experimental data and the kinetic analysis of volatile species, we developed a model that predicts a linear relationship between the reaction rate coefficient k and both the quadratic function of p(H2O) and the square root of p(H2). Moreover, the model predicted the partial pressure values for the predominant volatile species and the prediction was confirmed by the thermodynamic calculations, indicating the reliability of the model. We believe this model provides a foundation for designing a silicon refining process with a fast boron removal rate and low silicon loss.

  13. Material Balance And Reaction Kinetics Modeling For Penex Isomerization Process In Daura Refinery

    Directory of Open Access Journals (Sweden)

    Hamadi Adel Sharif

    2017-01-01

    Full Text Available Penex Deisohexanizer isomerization of light straight run naphtha is a significant process for petroleum refining and proved to be effective technology to produce gasoline components with a high octane number. Modeling of the chemical kinetic reactions is an important tool because it is a better tool for optimization of the experimental data into parameters used for industrial reactors. The present study deals on the isomerization process in Daura refinery. Material balance calculations were done mathematically on the unit for the kinetics prediction purpose. A kinetic mathematical model was derived for the prediction rate constants K1 and K2 and activation energy Ea at operating temperatures range 120-180°C. According to the model, the results show that with increasing of temperature leads to increased K1 directly, where the K2 values proportional inversely. The activation energy results show that Ea1(nC6

  14. Quantum field kinetics of QCD quark-gluon transport theory for light-cone dominated processes

    CERN Document Server

    Kinder-Geiger, Klaus

    1996-01-01

    A quantum kinetic formalism is developed to study the dynamical interplay of quantum and statistical-kinetic properties of non-equilibrium multi-parton systems produced in high-energy QCD processes. The approach provides the means to follow the quantum dynamics in both space-time and energy-momentum, starting from an arbitrary initial configuration of high-momentum quarks and gluons. Using a generalized functional integral representation and adopting the `closed-time-path' Green function techniques, a self-consistent set of equations of motions is obtained: a Ginzburg-Landau equation for a possible color background field, and Dyson-Schwinger equations for the 2-point functions of the gluon and quark fields. By exploiting the `two-scale nature' of light-cone dominated QCD processes, i.e. the separation between the quantum scale that specifies the range of short-distance quantum fluctuations, and the kinetic scale that characterizes the range of statistical binary inter- actions, the quantum-field equations of ...

  15. Making waves: Kinetic processes controlling surface evolution during low energy ion sputtering

    International Nuclear Information System (INIS)

    Chan, W.L.; Chason, Eric

    2007-01-01

    When collimated beams of low energy ions are used to bombard materials, the surface often develops a periodic pattern or ''ripple'' structure. Different types of patterns are observed to develop under different conditions, with characteristic features that depend on the substrate material, the ion beam parameters, and the processing conditions. Because the patterns develop spontaneously, without applying any external mask or template, their formation is the expression of a dynamic balance among fundamental surface kinetic processes, e.g., erosion of material from the surface, ion-induced defect creation, and defect-mediated evolution of the surface morphology. In recent years, a comprehensive picture of the different kinetic mechanisms that control the different types of patterns that form has begun to emerge. In this article, we provide a review of different mechanisms that have been proposed and how they fit together in terms of the kinetic regimes in which they dominate. These are grouped into regions of behavior dominated by the directionality of the ion beam, the crystallinity of the surface, the barriers to surface roughening, and nonlinear effects. In sections devoted to each type of behavior, we relate experimental observations of patterning in these regimes to predictions of continuum models and to computer simulations. A comparison between theory and experiment is used to highlight strengths and weaknesses in our understanding. We also discuss the patterning behavior that falls outside the scope of the current understanding and opportunities for advancement

  16. Oil extracted from spent coffee grounds for bio-hydrotreated diesel production

    International Nuclear Information System (INIS)

    Phimsen, Songphon; Kiatkittipong, Worapon; Yamada, Hiroshi; Tagawa, Tomohiko; Kiatkittipong, Kunlanan; Laosiripojana, Navadol; Assabumrungrat, Suttichai

    2016-01-01

    Highlights: • The spent coffee oil with high FFAs was hydrotreated to liquid biofuel. • Pd/C gave higher olefins while NiMo/γ-Al_2O_3 gave higher isoparaffins liquid products. • The diesel fuel fraction can have a cetane number as high as 80. • The physiochemical properties of diesel fraction comply with commercial standard. - Abstract: Oil extracted from spent coffee grounds is utilized as a renewable source for bio-hydrotreated fuel production. In the present work, oil yield up to 13% can be obtained by Soxhlet extraction with hexane as a solvent. As the extracted oil contained high content of free fatty acids (6.14%), therefore one step alkali-catalyzed for ester based biodiesel production is impractical. Hydrotreating of extracted oil was performed over two catalysts i.e. NiMo/γ-Al_2O_3 and Pd/C with different operating parameters i.e. reaction time, operating temperature, and H_2/oil. It was found that the reaction time of 2 h and the reaction temperature of 400 °C are favorable operating conditions. The liquid products mostly consisted of n-pentadecane and n-heptadecane, which contain one carbon atom shorter than the corresponding fatty acid (C_n_−_1) i.e. palmitic and stearic acid, respectively. Unfavorable cracking of diesel product is pronounced at high temperature and prolonged reaction time. In addition, although increased H_2/oil promoted overall reaction and hydrodeoxygenation activity (C_n_−_1/C_n decreased) for both catalysts, hydrocracking is enhanced over Pd/C, leading to significant increase in gasoline yield. Moreover, Pd/C gave higher olefin content in liquid product (22.3 wt%) than NiMo/γ-Al_2O_3 (4.8 wt%). However, NiMo/γ-Al_2O_3 shows higher isomerization activity. The amount of isoparaffins catalyzed by NiMo/γ-Al_2O_3 and Pd/C were 10.8 and 1.7 wt%, respectively. Physiochemical analysis of the diesel fraction exhibit satisfactory properties. The density and kinematic viscosity were consistent with the specification of

  17. Kinetic and spectral descriptions of autoionization phenomena associated with atomic processes in plasmas

    Science.gov (United States)

    Jacobs, Verne L.

    2017-06-01

    This investigation has been devoted to the theoretical description and computer modeling of atomic processes giving rise to radiative emission in energetic electron and ion beam interactions and in laboratory plasmas. We are also interested in the effects of directed electron and ion collisions and of anisotropic electric and magnetic fields. In the kinetic-theory description, we treat excitation, de-excitation, ionization, and recombination in electron and ion encounters with partially ionized atomic systems, including the indirect contributions from processes involving autoionizing resonances. These fundamental collisional and electromagnetic interactions also provide particle and photon transport mechanisms. From the spectral perspective, the analysis of atomic radiative emission can reveal detailed information on the physical properties in the plasma environment, such as non-equilibrium electron and charge-state distributions as well as electric and magnetic field distributions. In this investigation, a reduced-density-matrix formulation is developed for the microscopic description of atomic electromagnetic interactions in the presence of environmental (collisional and radiative) relaxation and decoherence processes. Our central objective is a fundamental microscopic description of atomic electromagnetic processes, in which both bound-state and autoionization-resonance phenomena can be treated in a unified and self-consistent manner. The time-domain (equation-of-motion) and frequency-domain (resolvent-operator) formulations of the reduced-density-matrix approach are developed in a unified and self-consistent manner. This is necessary for our ultimate goal of a systematic and self-consistent treatment of non-equilibrium (possibly coherent) atomic-state kinetics and high-resolution (possibly overlapping) spectral-line shapes. We thereby propose the introduction of a generalized collisional-radiative atomic-state kinetics model based on a reduced

  18. Bioleaching of spent hydro-processing catalyst using acidophilic bacteria and its kinetics aspect

    International Nuclear Information System (INIS)

    Mishra, Debaraj; Kim, Dong J.; Ralph, David E.; Ahn, Jong G.; Rhee, Young H.

    2008-01-01

    Bioleaching of metals from hazardous spent hydro-processing catalysts was attempted in the second stage after growing the bacteria with sulfur in the first stage. The first stage involved transformation of elemental sulfur particles to sulfuric acid through an oxidation process by acidophilic bacteria. In the second stage, the acidic medium was utilized for the leaching process. Nickel, vanadium and molybdenum contained within spent catalyst were leached from the solid materials to liquid medium by the action of sulfuric acid that was produced by acidophilic leaching bacteria. Experiments were conducted varying the reaction time, amount of spent catalysts, amount of elemental sulfur and temperature. At 50 g/L spent catalyst concentration and 20 g/L elemental sulfur, 88.3% Ni, 46.3% Mo, and 94.8% V were recovered after 7 days. Chemical leaching with commercial sulfuric acid of the similar amount that produced by bacteria was compared. Thermodynamic parameters were calculated and the nature of reaction was found to be exothermic. Leaching kinetics of the metals was represented by different reaction kinetic equations, however, only diffusion controlled model showed the best correlation here. During the whole process Mo showed low dissolution because of substantiate precipitation with leach residues as MoO 3 . Bioleach residues were characterized by EDX and XRD

  19. Bioleaching of spent hydro-processing catalyst using acidophilic bacteria and its kinetics aspect

    Energy Technology Data Exchange (ETDEWEB)

    Mishra, Debaraj [Mineral and Material Processing Division, Korea Institute of Geosciences and Mineral Resources, Daejeon 305-350 (Korea, Republic of); Department of Microbiology, Chungnam National University, Daejeon 305-764 (Korea, Republic of); Kim, Dong J. [Mineral and Material Processing Division, Korea Institute of Geosciences and Mineral Resources, Daejeon 305-350 (Korea, Republic of)], E-mail: djkim@kigam.re.kr; Ralph, David E. [AJ Parker CRC for Hydrometallurgy, Murdoch University, South Street Murdoch, Perth 6153 (Australia); Ahn, Jong G. [Mineral and Material Processing Division, Korea Institute of Geosciences and Mineral Resources, Daejeon 305-350 (Korea, Republic of); Rhee, Young H. [Department of Microbiology, Chungnam National University, Daejeon 305-764 (Korea, Republic of)

    2008-04-15

    Bioleaching of metals from hazardous spent hydro-processing catalysts was attempted in the second stage after growing the bacteria with sulfur in the first stage. The first stage involved transformation of elemental sulfur particles to sulfuric acid through an oxidation process by acidophilic bacteria. In the second stage, the acidic medium was utilized for the leaching process. Nickel, vanadium and molybdenum contained within spent catalyst were leached from the solid materials to liquid medium by the action of sulfuric acid that was produced by acidophilic leaching bacteria. Experiments were conducted varying the reaction time, amount of spent catalysts, amount of elemental sulfur and temperature. At 50 g/L spent catalyst concentration and 20 g/L elemental sulfur, 88.3% Ni, 46.3% Mo, and 94.8% V were recovered after 7 days. Chemical leaching with commercial sulfuric acid of the similar amount that produced by bacteria was compared. Thermodynamic parameters were calculated and the nature of reaction was found to be exothermic. Leaching kinetics of the metals was represented by different reaction kinetic equations, however, only diffusion controlled model showed the best correlation here. During the whole process Mo showed low dissolution because of substantiate precipitation with leach residues as MoO{sub 3}. Bioleach residues were characterized by EDX and XRD.

  20. Kinetics of spoilage fermentation in radurized fish and optimization of irradiation process

    International Nuclear Information System (INIS)

    Tukenmez, I.; Ersen, M.S.; Bakioglu, A.T.

    1997-01-01

    Kinetic studies on radiation-inactivation and the postirradiation growth of spoilage microorganisms during chill storage and their product formation inradurized fish were carried out. Anchovy (Engraulis encrasicholus) samples unirradiated, and those irradiated at 1,2 and 3 kGy doses of gamma radiation were stored at +2 o C for 21 days. Microbiological analyses of mesophilic, psycrophilic and total bacterial counts (TBC) and chemical analyses of trimethylamine (TMA) and total volatile bases (TVB) of the samples were done immediately after irradiation and periodically during storage. Radiation induced inactivations of bacteria were expressed with a first-order decreasing kinetics. A spoilage fermentation modeling was used to evaluate the quality control parameters of radurized fish in which the increase in TBC of survivor microorganisms during storage was described by a first-order growth with a lag phase and the production of TMA and TVB was described by a growth associated product formation. Examinations of the dose effects on the kinetic parameters resulted in that the relation between the product formation rate constants and the irradiation dose represented a parabolic function which was satisfactorily used to determine optimum irradiation dose. Optimum irradiation dose was found 1.719+- 0.471 kGy with TVB data resulting in an extended shelf-life of 15-16 days of fish. It is suggested that the kinetic evaluation method developed in this study may be substitute for or used with the analytical estimate in use comprising microbiological chemical and organoleptic controls for quality assessment and dose optimization of radurization processing of fish and other sea foods.(2 tab s. and 24 refs.)

  1. Process Analytical Technology for Advanced Process Control in Biologics Manufacturing with the Aid of Macroscopic Kinetic Modeling.

    Science.gov (United States)

    Kornecki, Martin; Strube, Jochen

    2018-03-16

    Productivity improvements of mammalian cell culture in the production of recombinant proteins have been made by optimizing cell lines, media, and process operation. This led to enhanced titers and process robustness without increasing the cost of the upstream processing (USP); however, a downstream bottleneck remains. In terms of process control improvement, the process analytical technology (PAT) initiative, initiated by the American Food and Drug Administration (FDA), aims to measure, analyze, monitor, and ultimately control all important attributes of a bioprocess. Especially, spectroscopic methods such as Raman or near-infrared spectroscopy enable one to meet these analytical requirements, preferably in-situ. In combination with chemometric techniques like partial least square (PLS) or principal component analysis (PCA), it is possible to generate soft sensors, which estimate process variables based on process and measurement models for the enhanced control of bioprocesses. Macroscopic kinetic models can be used to simulate cell metabolism. These models are able to enhance the process understanding by predicting the dynamic of cells during cultivation. In this article, in-situ turbidity (transmission, 880 nm) and ex-situ Raman spectroscopy (785 nm) measurements are combined with an offline macroscopic Monod kinetic model in order to predict substrate concentrations. Experimental data of Chinese hamster ovary cultivations in bioreactors show a sufficiently linear correlation (R² ≥ 0.97) between turbidity and total cell concentration. PLS regression of Raman spectra generates a prediction model, which was validated via offline viable cell concentration measurement (RMSE ≤ 13.82, R² ≥ 0.92). Based on these measurements, the macroscopic Monod model can be used to determine different process attributes, e.g., glucose concentration. In consequence, it is possible to approximately calculate (R² ≥ 0.96) glucose concentration based on online cell

  2. Process Analytical Technology for Advanced Process Control in Biologics Manufacturing with the Aid of Macroscopic Kinetic Modeling

    Directory of Open Access Journals (Sweden)

    Martin Kornecki

    2018-03-01

    Full Text Available Productivity improvements of mammalian cell culture in the production of recombinant proteins have been made by optimizing cell lines, media, and process operation. This led to enhanced titers and process robustness without increasing the cost of the upstream processing (USP; however, a downstream bottleneck remains. In terms of process control improvement, the process analytical technology (PAT initiative, initiated by the American Food and Drug Administration (FDA, aims to measure, analyze, monitor, and ultimately control all important attributes of a bioprocess. Especially, spectroscopic methods such as Raman or near-infrared spectroscopy enable one to meet these analytical requirements, preferably in-situ. In combination with chemometric techniques like partial least square (PLS or principal component analysis (PCA, it is possible to generate soft sensors, which estimate process variables based on process and measurement models for the enhanced control of bioprocesses. Macroscopic kinetic models can be used to simulate cell metabolism. These models are able to enhance the process understanding by predicting the dynamic of cells during cultivation. In this article, in-situ turbidity (transmission, 880 nm and ex-situ Raman spectroscopy (785 nm measurements are combined with an offline macroscopic Monod kinetic model in order to predict substrate concentrations. Experimental data of Chinese hamster ovary cultivations in bioreactors show a sufficiently linear correlation (R2 ≥ 0.97 between turbidity and total cell concentration. PLS regression of Raman spectra generates a prediction model, which was validated via offline viable cell concentration measurement (RMSE ≤ 13.82, R2 ≥ 0.92. Based on these measurements, the macroscopic Monod model can be used to determine different process attributes, e.g., glucose concentration. In consequence, it is possible to approximately calculate (R2 ≥ 0.96 glucose concentration based on online cell

  3. A KINETIC MODEL FOR H2O2/UV PROCESS IN A COMPLETELY MIXED BATCH REACTOR. (R825370C076)

    Science.gov (United States)

    A dynamic kinetic model for the advanced oxidation process (AOP) using hydrogen peroxide and ultraviolet irradiation (H2O2/UV) in a completely mixed batch reactor (CMBR) is developed. The model includes the known elementary chemical and photochemical reac...

  4. Numerical studies of spray combustion processes of palm oil biodiesel and diesel fuels using reduced chemical kinetic mechanisms

    KAUST Repository

    Kuti, Olawole; Sarathy, Mani; Nishida, Keiya; Roberts, William L.

    2014-01-01

    Spray combustion processes of palm oil biodiesel (PO) and conventional diesel fuels were simulated using the CONVERGE CFD code. Thermochemical and reaction kinetic data (115 species and 460 reactions) by Luo et al. (2012) and Lu et al. (2009) (68

  5. Quantum field kinetics of QCD: Quark-gluon transport theory for light-cone-dominated processes

    International Nuclear Information System (INIS)

    Geiger, K.

    1996-01-01

    A quantum-kinetic formalism is developed to study the dynamical interplay of quantum and statistical-kinetic properties of nonequilibrium multiparton systems produced in high-energy QCD processes. The approach provides the means to follow the quantum dynamics in both space-time and energy-momentum, starting from an arbitrary initial configuration of high-momentum quarks and gluons. Using a generalized functional integral representation and adopting the open-quote open-quote closed-time-path close-quote close-quote Green function techniques, a self-consistent set of equations of motions is obtained: a Ginzburg-Landau equation for a possible color background field, and Dyson-Schwinger equations for the two-point functions of the gluon and quark fields. By exploiting the open-quote open-quote two-scale nature close-quote close-quote of light-cone-dominated QCD processes, i.e., the separation between the quantum scale that specifies the range of short-distance quantum fluctuations, and the kinetic scale that characterizes the range of statistical binary interactions, the quantum field equations of motion are converted into a corresponding set of open-quote open-quote renormalization equations close-quote close-quote and open-quote open-quote transport equations.close-quote close-quote The former describe renormalization and dissipation effects through the evolution of the spectral density of individual, dressed partons, whereas the latter determine the statistical occurrence of scattering processes among these dressed partons. The renormalization equations and the transport equations are coupled, and, hence, must be solved self-consistently. This amounts to evolving the multiparton system, from a specified initial configuration, in time and full seven-dimensional phase space, constrained by the Heisenberg uncertainty principle. (Abstract Truncated)

  6. A kinetic reaction model for biomass pyrolysis processes in Aspen Plus

    International Nuclear Information System (INIS)

    Peters, Jens F.; Banks, Scott W.; Bridgwater, Anthony V.; Dufour, Javier

    2017-01-01

    Highlights: • Predictive kinetic reaction model applicable to any lignocellulosic feedstock. • Calculates pyrolysis yields and product composition as function of reactor conditions. • Detailed modelling of product composition (33 model compounds for the bio-oil). • Good agreement with literature regarding yield curves and product composition. • Successful validation with pyrolysis experiments in bench scale fast pyrolysis rig. - Abstract: This paper presents a novel kinetic reaction model for biomass pyrolysis processes. The model is based on the three main building blocks of lignocellulosic biomass, cellulose, hemicellulose and lignin and can be readily implemented in Aspen Plus and easily adapted to other process simulation software packages. It uses a set of 149 individual reactions that represent the volatilization, decomposition and recomposition processes of biomass pyrolysis. A linear regression algorithm accounts for the secondary pyrolysis reactions, thus allowing the calculation of slow and intermediate pyrolysis reactions. The bio-oil is modelled with a high level of detail, using up to 33 model compounds, which allows for a comprehensive estimation of the properties of the bio-oil and the prediction of further upgrading reactions. After showing good agreement with existing literature data, our own pyrolysis experiments are reported for validating the reaction model. A beech wood feedstock is subjected to pyrolysis under well-defined conditions at different temperatures and the product yields and compositions are determined. Reproducing the experimental pyrolysis runs with the simulation model, a high coincidence is found for the obtained fraction yields (bio-oil, char and gas), for the water content and for the elemental composition of the pyrolysis products. The kinetic reaction model is found to be suited for predicting pyrolysis yields and product composition for any lignocellulosic biomass feedstock under typical pyrolysis conditions

  7. Role of hydrotreating products in deposition of fine particles in reactors

    Energy Technology Data Exchange (ETDEWEB)

    Wang, S.; Chung, K.; Gray, M.R. [University of Alberta, Edmonton, AB (Canada). Dept. of Chemical and Materials Engineering

    2001-06-11

    Hydrotreating reactions may affect the deposition of fine particles, which can eventually lead to reactor plugging. The deposition of fine particles from gas oil was measured in an internally recirculating reactor at 375{degree}C under hydrogen. H{sub 2}S from hydrodesulfurization would convert corrosion products to metal sulfides. Iron sulfide deposited rapidly in the packed bed because the mineral surface did not retain a stabilizing layer of asphaltenic material. Addition of water, to test the role of hydrodeoxygenation, doubled the deposition of clay particles by reducing the surface coating of organic material. Neither ammonia or quinoline had any effect on particle deposition, therefore, hydrodenitrogenation did not affect particle behavior. 16 refs., 4 figs., 3 tabs.

  8. Synthesis of carbon nanotubes by CCVD of natural gas using hydrotreating catalysts

    Directory of Open Access Journals (Sweden)

    Ahmed E. Awadallah

    2012-12-01

    Full Text Available Carbon nanotubes have been successfully synthesized using the catalytic chemical vapor deposition (CCVD technique over typical refining hydrotreating catalysts (hydrodesulfurization and hydrodenitrogenation containing Ni–Mo and Co–Mo supported on Al2O3 catalysts at 700°C in a fixed bed horizontal reactor using natural gas as a carbon source. The catalysts and the as-grown CNTs were characterized by transmission electron microscopy, HRTEM, X-ray diffraction patterns, EDX and TGA–DTG. The obtained data clarified that the Ni–Mo catalyst gives higher yield, higher purity and selectivity for CNTs compared to Co–Mo catalyst. XRD, TEM and TGA reveal also that the Ni–Mo catalyst produces mostly CNTs with different diameters whereas the Co–Mo catalyst produces largely amorphous carbon.

  9. Microwave irradiation enhances kinetics of the biomimetic process of hydroxyapatite nanocomposites

    International Nuclear Information System (INIS)

    Guha, Avijit; Nayar, Suprabha; Thatoi, H N

    2010-01-01

    In situ synthesized hydroxyapatite-poly(vinyl) alcohol nanocomposite was subjected to microwave irradiation, post synthesis. Interestingly, the aging time of 1 week required for the normal biomimetic process was reduced to 1 h post microwave irradiation, as characterized by x-ray powder diffraction and transmission electron microscopy. The surface topography shows the tendency of tubules to cross-link with the help of microwave energy. The microwave energy seems to provide a directional pull to the polymer chains which could have led to an enhancement of the kinetics of phase formation. (communication)

  10. New kinetic insight into the spontaneous oxidation process of lithium in air by EPMA

    Energy Technology Data Exchange (ETDEWEB)

    Otero, Manuel [IFEG, Facultad de Matemáticas, Astronomía y Física, Universidad Nacional de Córdoba, Córdoba (Argentina); INFICQ, Departamento de Matemáticas y Física, Facultad de Ciencias Químicas, Universidad Nacional de Córdoba, Córdoba (Argentina); Lener, German [INFAP, Facultad de Ciencias Físico Matemáticas y Naturales, Universidad Nacional de San Luis, San Luis (Argentina); Trincavelli, Jorge, E-mail: trincavelli@famaf.unc.edu.ar [IFEG, Facultad de Matemáticas, Astronomía y Física, Universidad Nacional de Córdoba, Córdoba (Argentina); Barraco, Daniel [IFEG, Facultad de Matemáticas, Astronomía y Física, Universidad Nacional de Córdoba, Córdoba (Argentina); Nazzarro, Marcelo Sandro; Furlong, Octavio [INFAP, Facultad de Ciencias Físico Matemáticas y Naturales, Universidad Nacional de San Luis, San Luis (Argentina); Leiva, Ezequiel Pedro Marcos [INFICQ, Departamento de Matemáticas y Física, Facultad de Ciencias Químicas, Universidad Nacional de Córdoba, Córdoba (Argentina)

    2016-10-15

    Highlights: • EPMA measurements and Monte Carlo simulations were applied to study the corrosion process of Li in air. • The kinetic mechanism of corrosion was discussed. • A diffusion process of water through LiOH was found and quantitatively studied. - Abstract: The exposure of metallic lithium to ambient air produces a fast corrosion reaction of the surface that continues to the bulk of the material. This spontaneous process was explored by means of X-ray Photoelectron Spectroscopy (XPS) and Electron Probe Micro-Analysis (EPMA). The combination of these techniques and Monte Carlo simulations allowed observing the formation of a film of lithium hydroxide (LiOH) and studying the growth within the material during the first 300 s. The corrosion is mainly due to the reaction of lithium with water and the diffusion of water through the growing LiOH film is the rate determining step. On the basis of a kinetic analysis we studied the mechanism of reaction and inferred a diffusion coefficient of D = (5.1 ± 0.4) × 10{sup −12} cm{sup 2}/s in agreement with results from the literature obtained using different techniques.

  11. Prediction of Proper Temperatures for the Hot Stamping Process Based on the Kinetics Models

    Science.gov (United States)

    Samadian, P.; Parsa, M. H.; Mirzadeh, H.

    2015-02-01

    Nowadays, the application of kinetics models for predicting microstructures of steels subjected to thermo-mechanical treatments has increased to minimize direct experimentation, which is costly and time consuming. In the current work, the final microstructures of AISI 4140 steel sheets after the hot stamping process were predicted using the Kirkaldy and Li kinetics models combined with new thermodynamically based models in order for the determination of the appropriate process temperatures. In this way, the effect of deformation during hot stamping on the Ae3, Acm, and Ae1 temperatures was considered, and then the equilibrium volume fractions of phases at different temperatures were calculated. Moreover, the ferrite transformation rate equations of the Kirkaldy and Li models were modified by a term proposed by Åkerström to consider the influence of plastic deformation. Results showed that the modified Kirkaldy model is satisfactory for the determination of appropriate austenitization temperatures for the hot stamping process of AISI 4140 steel sheets because of agreeable microstructure predictions in comparison with the experimental observations.

  12. Non-isothermal kinetic studies on co-processing of olive residue and polypropylene

    International Nuclear Information System (INIS)

    Aboulkas, A.; El Harfi, K.; El Bouadili, A.

    2008-01-01

    Co-processing of olive residue with polypropylene was performed in a thermogravimetric analyzer (TGA) reaction system in a nitrogen atmosphere with a view to comparing the process of the mixture with those of the individual components. Experiments were conducted at different heating rates of 2, 10, 20 and 50 K min -1 in the temperature range of 300-975 K based on the results obtained, three thermal stages were identified during the thermal degradation. The first two were dominated by olive residue pyrolysis, while the third was linked to polypropylene pyrolysis, which occurred at much higher temperatures. Discrepancies between the experimental and calculated TG/DTG profiles were considered as a measurement of the extent of interactions occurring on co-pyrolysis. The maximum degradation temperature of each component in the mixture was higher than those of the individual components alone; thus, an increase in thermal stability was expected. The kinetic processing of thermogravimetric data was conducted using the Friedman method

  13. Evaluation of silage-fed biogas process performance using microbiological and kinetic methods

    Energy Technology Data Exchange (ETDEWEB)

    Jarvis, Aa

    1996-10-01

    In this study, different kinetic and microbiological methods were used to evaluate the growth and activity of key groups of bacteria degrading ley silage in one-phase and two-phase biogas processes. Emphasis was placed on studying the dynamic behaviour of different trophic groups resulting from the initiation of liquid recirculation in the processes. The microbiological methods included microscopy and most probable number (MPN) counts with different substrates. The kinetic methods included measurements of specific methanogenic activity (SMA) with acetate and H{sub 2}/CO{sub 2} as substrates, batch assays with trace element additions and measurement of conversion rates of mannitol and lactate in the digesters. In general, the initiation of liquid recirculation at first promoted the growth and/or activity of several trophic groups of bacteria, such as butyrate and propionate degraders and acetotrophic and hydrogenotrophic methanogens in the liquefaction/acidogenesis reactors of the two-phase processes. This was probably mainly due to the increased pH. However, after some time of liquid recirculation, an inhibition of some bacterial groups occurred, such as propionate degraders and methanogens in the methanogenic reactors of two-phase processes. This was probably due to increased concentrations of salts and free ammonia. The batch assays proved to be valuable tools in process optimization by the addition of trace elements. Here, the addition of cobalt significantly increased methane production from acetate. In this study, a more comprehensive understanding of the process behaviour in response to the initiation of liquid recirculation was achieved which could not have been obtained by only monitoring routine parameters such as pH, methane production and concentrations of organic acids and salts. 120 refs, 4 figs, 1 tab

  14. Dynamic Model of Basic Oxygen Steelmaking Process Based on Multi-zone Reaction Kinetics: Model Derivation and Validation

    Science.gov (United States)

    Rout, Bapin Kumar; Brooks, Geoff; Rhamdhani, M. Akbar; Li, Zushu; Schrama, Frank N. H.; Sun, Jianjun

    2018-04-01

    A multi-zone kinetic model coupled with a dynamic slag generation model was developed for the simulation of hot metal and slag composition during the basic oxygen furnace (BOF) operation. The three reaction zones (i) jet impact zone, (ii) slag-bulk metal zone, (iii) slag-metal-gas emulsion zone were considered for the calculation of overall refining kinetics. In the rate equations, the transient rate parameters were mathematically described as a function of process variables. A micro and macroscopic rate calculation methodology (micro-kinetics and macro-kinetics) were developed to estimate the total refining contributed by the recirculating metal droplets through the slag-metal emulsion zone. The micro-kinetics involves developing the rate equation for individual droplets in the emulsion. The mathematical models for the size distribution of initial droplets, kinetics of simultaneous refining of elements, the residence time in the emulsion, and dynamic interfacial area change were established in the micro-kinetic model. In the macro-kinetics calculation, a droplet generation model was employed and the total amount of refining by emulsion was calculated by summing the refining from the entire population of returning droplets. A dynamic FetO generation model based on oxygen mass balance was developed and coupled with the multi-zone kinetic model. The effect of post-combustion on the evolution of slag and metal composition was investigated. The model was applied to a 200-ton top blowing converter and the simulated value of metal and slag was found to be in good agreement with the measured data. The post-combustion ratio was found to be an important factor in controlling FetO content in the slag and the kinetics of Mn and P in a BOF process.

  15. Kinetics of physico-chemical processes during intensive mechanical processing of ZnO-MnO{sub 2} powder mixture

    Energy Technology Data Exchange (ETDEWEB)

    Kakazey, M.; Vlasova, M.; Dominguez-Patino, M. [CIICAp-Universidad Autonoma del Estado de Morelos, Cuernavaca (Mexico); Juarez-Arellano, E.A., E-mail: eajuarez@unpa.edu.mx [Universidad del Papaloapan, Tuxtepec, Oaxaca (Mexico); Bykov, A. [Institute for Problems of Materials Science of NASU, Kyiv (Ukraine); Leon, I. [CIQ-Universidad Autonoma del Estado de Morelos, Cuernavaca (Mexico); Siqueiros-Diaz, A. [FCQI-Universidad Autonoma del Estado de Morelos, Cuernavaca (Mexico)

    2011-10-15

    Experimental results of electron paramagnetic resonance spectra, X-ray diffraction, scanning electron microscopy and infrared spectroscopy demonstrate that the kinetic of the physical and chemical processes that takes place during prolonged intensive mechanical processing (MP, 03120min) of powder mixtures of 50%wt ZnO+50%wt MnO{sub 2} can be described as a three stage process. (1) 030min, particles destruction, formation of superficial defects, fast increment of sample average temperature (from 290 to {approx}600K) and annealing of defects with the lowest energy of activation E{sub ac}. (2) 30390min, further particle destruction, slow increment of sample average temperature (from {approx}600 to {approx}700K), formation and growth of a very disordered layer of {beta}-MnO{sub 2} around ZnO particles, dehydration of MnO{sub 2}, formation of solid solution of Mn{sup 2+} ions in ZnO, formation of nano-quasiamorphous states in the ZnO-MnO{sub 2} mixture and onset of the formation of the ZnMnO{sub 3} phase. (3) 3903120min, the sample average temperature remains constant ({approx}700K), the reaction is completed and the spinel ZnMnO{sub 3} phase with a unit cell a=8.431(1) A and space group Fd3-barm is the only phase present in the sample. No ferromagnetism at room temperature was detected in this study. - Highlights: > The kinetics during mechanical processing of ZnO-MnO{sub 2} samples is a three stage process. > First stage, reduction of crystallites size and accumulation of defects. > Second stage, nano-quasiamorphous states formation and onset of the ZnMnO{sub 3} phase. > Third stage, complete reaction to the spinel ZnMnO{sub 3} phase.

  16. Kinetics of physico-chemical processes during intensive mechanical processing of ZnO-MnO2 powder mixture

    International Nuclear Information System (INIS)

    Kakazey, M.; Vlasova, M.; Dominguez-Patino, M.; Juarez-Arellano, E.A.; Bykov, A.; Leon, I.; Siqueiros-Diaz, A.

    2011-01-01

    Experimental results of electron paramagnetic resonance spectra, X-ray diffraction, scanning electron microscopy and infrared spectroscopy demonstrate that the kinetic of the physical and chemical processes that takes place during prolonged intensive mechanical processing (MP, 0 MP >3120min) of powder mixtures of 50%wt ZnO+50%wt MnO 2 can be described as a three stage process. (1) 0 MP >30min, particles destruction, formation of superficial defects, fast increment of sample average temperature (from 290 to ∼600K) and annealing of defects with the lowest energy of activation E ac . (2) 30 MP >390min, further particle destruction, slow increment of sample average temperature (from ∼600 to ∼700K), formation and growth of a very disordered layer of β-MnO 2 around ZnO particles, dehydration of MnO 2 , formation of solid solution of Mn 2+ ions in ZnO, formation of nano-quasiamorphous states in the ZnO-MnO 2 mixture and onset of the formation of the ZnMnO 3 phase. (3) 390 MP >3120min, the sample average temperature remains constant (∼700K), the reaction is completed and the spinel ZnMnO 3 phase with a unit cell a=8.431(1) A and space group Fd3-barm is the only phase present in the sample. No ferromagnetism at room temperature was detected in this study. - Highlights: → The kinetics during mechanical processing of ZnO-MnO 2 samples is a three stage process. → First stage, reduction of crystallites size and accumulation of defects. → Second stage, nano-quasiamorphous states formation and onset of the ZnMnO 3 phase. → Third stage, complete reaction to the spinel ZnMnO 3 phase.

  17. Kinetic modelling of a diesel-polluted clayey soil bioremediation process

    Energy Technology Data Exchange (ETDEWEB)

    Fernández, Engracia Lacasa; Merlo, Elena Moliterni [Chemical Engineering Department, Research Institute for Chemical and Environmental Technology (ITQUIMA), University of Castilla La Mancha, 13071 Ciudad Real (Spain); Mayor, Lourdes Rodríguez [National Institute for Hydrogen Research, C/Fernando el Santo, 13500 Puertollano (Spain); Camacho, José Villaseñor, E-mail: jose.villasenor@uclm.es [Chemical Engineering Department, Research Institute for Chemical and Environmental Technology (ITQUIMA), University of Castilla La Mancha, 13071 Ciudad Real (Spain)

    2016-07-01

    A mathematical model is proposed to describe a diesel-polluted clayey soil bioremediation process. The reaction system under study was considered a completely mixed closed batch reactor, which initially contacted a soil matrix polluted with diesel hydrocarbons, an aqueous liquid-specific culture medium and a microbial inoculation. The model coupled the mass transfer phenomena and the distribution of hydrocarbons among four phases (solid, S; water, A; non-aqueous liquid, NAPL; and air, V) with Monod kinetics. In the first step, the model simulating abiotic conditions was used to estimate only the mass transfer coefficients. In the second step, the model including both mass transfer and biodegradation phenomena was used to estimate the biological kinetic and stoichiometric parameters. In both situations, the model predictions were validated with experimental data that corresponded to previous research by the same authors. A correct fit between the model predictions and the experimental data was observed because the modelling curves captured the major trends for the diesel distribution in each phase. The model parameters were compared to different previously reported values found in the literature. Pearson correlation coefficients were used to show the reproducibility level of the model. - Highlights: • A mathematical model is proposed to describe a soil bioremediation process. • The model couples mass transfer phenomena among phases with biodegradation. • Model predictions were validated with previous data reported by the authors. • A correct fit and correlation coefficients were observed.

  18. Functional Enzyme-Based Approach for Linking Microbial Community Functions with Biogeochemical Process Kinetics

    Energy Technology Data Exchange (ETDEWEB)

    Li, Minjing [School; Qian, Wei-jun [Pacific Northwest National Laboratory, Richland, Washington 99354, United States; Gao, Yuqian [Pacific Northwest National Laboratory, Richland, Washington 99354, United States; Shi, Liang [School; Liu, Chongxuan [Pacific Northwest National Laboratory, Richland, Washington 99354, United States; School

    2017-09-28

    The kinetics of biogeochemical processes in natural and engineered environmental systems are typically described using Monod-type or modified Monod-type models. These models rely on biomass as surrogates for functional enzymes in microbial community that catalyze biogeochemical reactions. A major challenge to apply such models is the difficulty to quantitatively measure functional biomass for constraining and validating the models. On the other hand, omics-based approaches have been increasingly used to characterize microbial community structure, functions, and metabolites. Here we proposed an enzyme-based model that can incorporate omics-data to link microbial community functions with biogeochemical process kinetics. The model treats enzymes as time-variable catalysts for biogeochemical reactions and applies biogeochemical reaction network to incorporate intermediate metabolites. The sequences of genes and proteins from metagenomes, as well as those from the UniProt database, were used for targeted enzyme quantification and to provide insights into the dynamic linkage among functional genes, enzymes, and metabolites that are necessary to be incorporated in the model. The application of the model was demonstrated using denitrification as an example by comparing model-simulated with measured functional enzymes, genes, denitrification substrates and intermediates

  19. Simplified modeling of simultaneous reaction kinetics of carbon oxidation and nitrification in biofilm processes

    Energy Technology Data Exchange (ETDEWEB)

    Tsuneda, S.; Auresenia, J.; Hibiya, K.; Hirata, A. [Waseda University, Department of Chemical Engineering, 3-4-1 Ohkubo, Shinjuku-ku, Tokyo 169-8555 (Japan)

    2004-06-01

    Batch experiments with varying initial substrate concentrations and biomass volumes were performed in a three-phase fluidized bed biofilm reactor treating simulated domestic wastewater to study the simultaneous carbon oxidation and nitrification in the biofilm process. A simplified mass balance equation for the biofilm was proposed and five different kinetic rate equations were used to match the actual data. The kinetic parameters were obtained by nonlinear regression analysis on a set of two differential equations representing the simultaneous carbon oxidation and nitrification. The competitive inhibition model incorporating the effects of total organic carbon (TOC) concentrations on nitrification rates was the best-suited model based on the average r{sup 2}. In this model, oxygen concentration and its affinity constants were not included. Instead, it was assumed that the rate of carbon oxidation is independent of the NH{sub 4}{sup +}-N, while nitrification is affected by TOC. The number of parameters was successfully minimized without reducing its ability to accurately predict the bulk concentration time course, which would reduce computational complexity and possibly enhance the availability for an actual wastewater treatment process. (Abstract Copyright [2004], Wiley Periodicals, Inc.)

  20. Kinetic modelling of a diesel-polluted clayey soil bioremediation process

    International Nuclear Information System (INIS)

    Fernández, Engracia Lacasa; Merlo, Elena Moliterni; Mayor, Lourdes Rodríguez; Camacho, José Villaseñor

    2016-01-01

    A mathematical model is proposed to describe a diesel-polluted clayey soil bioremediation process. The reaction system under study was considered a completely mixed closed batch reactor, which initially contacted a soil matrix polluted with diesel hydrocarbons, an aqueous liquid-specific culture medium and a microbial inoculation. The model coupled the mass transfer phenomena and the distribution of hydrocarbons among four phases (solid, S; water, A; non-aqueous liquid, NAPL; and air, V) with Monod kinetics. In the first step, the model simulating abiotic conditions was used to estimate only the mass transfer coefficients. In the second step, the model including both mass transfer and biodegradation phenomena was used to estimate the biological kinetic and stoichiometric parameters. In both situations, the model predictions were validated with experimental data that corresponded to previous research by the same authors. A correct fit between the model predictions and the experimental data was observed because the modelling curves captured the major trends for the diesel distribution in each phase. The model parameters were compared to different previously reported values found in the literature. Pearson correlation coefficients were used to show the reproducibility level of the model. - Highlights: • A mathematical model is proposed to describe a soil bioremediation process. • The model couples mass transfer phenomena among phases with biodegradation. • Model predictions were validated with previous data reported by the authors. • A correct fit and correlation coefficients were observed.

  1. Hydrothermal decomposition of industrial jarosite in alkaline media: The rate determining step of the process kinetics

    Directory of Open Access Journals (Sweden)

    González-Ibarra A.A.

    2016-01-01

    Full Text Available This work examines the role of NaOH and Ca(OH2 on the hydrothermal decomposition of industrial jarosite deposited by a Mexican company in a tailings dam. The industrial jarosite is mainly composed by natrojarosite and contains 150 g Ag/t, showing a narrow particle size distribution, as revealed by XRD, fire assay, SEM-EDS and laser-diffraction analysis. The effect of the pH, when using NaOH or Ca(OH2 as alkalinizing agent was studied by carrying out decomposition experiments at different pH values and 60°C in a homogeneous size particle system (pH = 8, 9, 10 and 11 and in a heterogeneous size particle system (pH = 11. Also, the kinetic study of the process and the controlling step of the decomposition reaction when NaOH and Ca(OH2 are used was determined by fitting the data obtained to the shrinking core model for spherical particles of constant size. These results, supported by chemical (EDS, morphological (SEM and mapping of elements (EDS analysis of a partially reacted jarosite particle allowed to conclude that when NaOH is used, the process kinetics is controlled by the chemical reaction and when Ca(OH2 is used, the rate determining step is changed to a diffusion control through a layer of solid products.

  2. Revealing chemical processes and kinetics of drug action within single living cells via plasmonic Raman probes.

    Science.gov (United States)

    Li, Shan-Shan; Guan, Qi-Yuan; Meng, Gang; Chang, Xiao-Feng; Wei, Ji-Wu; Wang, Peng; Kang, Bin; Xu, Jing-Juan; Chen, Hong-Yuan

    2017-05-23

    Better understanding the drug action within cells may extend our knowledge on drug action mechanisms and promote new drugs discovery. Herein, we studied the processes of drug induced chemical changes on proteins and nucleic acids in human breast adenocarcinoma (MCF-7) cells via time-resolved plasmonic-enhanced Raman spectroscopy (PERS) in combination with principal component analysis (PCA). Using three popular chemotherapy drugs (fluorouracil, cisplatin and camptothecin) as models, chemical changes during drug action process were clearly discriminated. Reaction kinetics related to protein denaturation, conformational modification, DNA damage and their associated biomolecular events were calculated. Through rate constants and reaction delay times, the different action modes of these drugs could be distinguished. These results may provide vital insights into understanding the chemical reactions associated with drug-cell interactions.

  3. Kinetics of the Leaching Process of an Australian Gibbsitic Bauxite by Hydrochloric Acid

    Directory of Open Access Journals (Sweden)

    Aichun Zhao

    2016-01-01

    Full Text Available Gibbsitic bauxite from Australia was leached by hydrochloric acid in this work. Analysis on kinetics for the extraction of Al2O3 was quantitatively studied. It was concluded that the hydrochloric acid leaching process of gibbsitic bauxite was controlled by chemical reaction. Moreover, the mechanism for the dissolution followed the equation, ln⁡k=39.44-1.66×104(1/T, with an apparent activation energy of 137.90 kJ/mol, according to the equation of k=Ae-Ea/RT. This work aims to provide a good theory support for the process control by using a new method of alumina production from the low grade bauxite.

  4. Kinetics of oxygen adsorption on ZnS nanoparticles synthesized by precipitation process

    Directory of Open Access Journals (Sweden)

    Ahmadi Reza

    2016-06-01

    Full Text Available ZnS nanoparticles were synthesized through a one-step precipitation process. Effect of time and temperature on the formation reaction was investigated. The synthesized samples were characterized by X-ray diffraction (XRD, ultraviolet (UV visible absorption and photoluminescence (PL spectrophotometry. Based on XRD and UV-Vis data, the particles produced at 70 °C had a mean particle size of about 5 nm. Increasing time and temperature of the synthesis reaction resulted in photoluminescence intensification. PL spectroscopy helped understanding the adsorption kinetics of oxygen on ZnS nanoparticles during the precipitation synthesis process. Fabrication of ZnS structures with appropriate oxygen adsorption capacity was suggested as a means of PL emission intensity control.

  5. Data on blueberry peroxidase kinetic characterization and stability towards thermal and high pressure processing

    Directory of Open Access Journals (Sweden)

    Netsanet Shiferaw Terefe

    2017-08-01

    Full Text Available The data presented in this article are related to a research article entitled ‘Thermal and high pressure inactivation kinetics of blueberry peroxidase’ (Terefe et al., 2017 [1]. In this article, we report original data on the activity of partially purified blueberry peroxidase at different concentrations of hydrogen peroxide and phenlylenediamine as substrates and the effects of thermal and high pressure processing on the activity of the enzyme. Data on the stability of the enzyme during thermal (at temperatures ranging from 40 to 80 °C and combined thermal-high pressure processing (100–690 MPa, 30–90 °C are included in this report. The data are presented in this format in order to facilitate comparison with data from other researchers and allow statistical analyses and modeling by others in the field.

  6. Kinetic models for nitrogen inhibition in ANAMMOX and nitrification process on deammonification system at room temperature.

    Science.gov (United States)

    De Prá, Marina C; Kunz, Airton; Bortoli, Marcelo; Scussiato, Lucas A; Coldebella, Arlei; Vanotti, Matias; Soares, Hugo M

    2016-02-01

    In this study were fitted the best kinetic model for nitrogen removal inhibition by ammonium and/or nitrite in three different nitrogen removal systems operated at 25 °C: a nitrifying system (NF) containing only ammonia oxidizing bacteria (AOB), an ANAMMOX system (AMX) containing only ANAMMOX bacteria, and a deammonification system (DMX) containing both AOB and ANAMMOX bacteria. NF system showed inhibition by ammonium and was best described by Andrews model. The AMX system showed a strong inhibition by nitrite and Edwards model presented a best system representation. For DMX system, the increased substrate concentration (until 1060 mg NH3-N/L) tested was not limiting for the ammonia consumption rate and the Monod model was the best model to describe this process. The AOB and ANAMMOX sludges combined in the DMX system displayed a better activity, substrate affinity and excellent substrate tolerance than in nitrifying and ANAMMOX process. Copyright © 2015 Elsevier Ltd. All rights reserved.

  7. Kinetics of the process of formation and high-temperature oxidation of electrospark coatings on steel

    International Nuclear Information System (INIS)

    Verkhoturov, A.D.; Chiplik, V.N.; Egorov, F.F.; Lavrenko, V.A.; Podchernyaeva, I.A.; Shemet, V.Z.

    1986-01-01

    This work is a study of the kinetics of formation and of the heat resistance of electrospark coatings based on the composite TiB 2 -Mo with varying molybdenum content. In the process of electrospark alloying they measured the specific erosion of the anode and the increase in weight of the cathode with an accuracy not worse than 5%. Electrospark coatings of TiB 2 -Mo on steel 45 are marked by improved scaling resistance at temperatures above 900 C. Their scaling resistance and also the effectiveness of the process of electrospark alloying increase with increasing content of the phase B-MoB in the coating because molybdenum borate forms during its high-temperature oxidation. Illustrations and table are included

  8. Fermi-level effects in semiconductor processing: A modeling scheme for atomistic kinetic Monte Carlo simulators

    Science.gov (United States)

    Martin-Bragado, I.; Castrillo, P.; Jaraiz, M.; Pinacho, R.; Rubio, J. E.; Barbolla, J.; Moroz, V.

    2005-09-01

    Atomistic process simulation is expected to play an important role for the development of next generations of integrated circuits. This work describes an approach for modeling electric charge effects in a three-dimensional atomistic kinetic Monte Carlo process simulator. The proposed model has been applied to the diffusion of electrically active boron and arsenic atoms in silicon. Several key aspects of the underlying physical mechanisms are discussed: (i) the use of the local Debye length to smooth out the atomistic point-charge distribution, (ii) algorithms to correctly update the charge state in a physically accurate and computationally efficient way, and (iii) an efficient implementation of the drift of charged particles in an electric field. High-concentration effects such as band-gap narrowing and degenerate statistics are also taken into account. The efficiency, accuracy, and relevance of the model are discussed.

  9. Kinetics of two-stage fermentation process for the production of hydrogen

    Energy Technology Data Exchange (ETDEWEB)

    Nath, Kaushik [Department of Chemical Engineering, G.H. Patel College of Engineering and Technology, Vallabh Vidyanagar 388 120, Gujarat (India); Muthukumar, Manoj; Kumar, Anish; Das, Debabrata [Fermentation Technology Laboratory, Department of Biotechnology, Indian Institute of Technology, Kharagpur 721302 (India)

    2008-02-15

    Two-stage process described in the present work is a combination of dark and photofermentation in a sequential batch mode. In the first stage glucose is fermented to acetate, CO{sub 2} and H{sub 2} in an anaerobic dark fermentation by Enterobacter cloacae DM11. This is followed by a successive second stage where acetate is converted to H{sub 2} and CO{sub 2} in a photobioreactor by photosynthetic bacteria, Rhodobacter sphaeroides O.U. 001. The yield of hydrogen in the first stage was about 3.31molH{sub 2}(molglucose){sup -1} (approximately 82% of theoretical) and that in the second stage was about 1.5-1.72molH{sub 2}(molaceticacid){sup -1} (approximately 37-43% of theoretical). The overall yield of hydrogen in two-stage process considering glucose as preliminary substrate was found to be higher compared to a single stage process. Monod model, with incorporation of substrate inhibition term, has been used to determine the growth kinetic parameters for the first stage. The values of maximum specific growth rate ({mu} {sub max}) and K{sub s} (saturation constant) were 0.398h{sup -1} and 5.509gl{sup -1}, respectively, using glucose as substrate. The experimental substrate and biomass concentration profiles have good resemblance with those obtained by kinetic model predictions. A model based on logistic equation has been developed to describe the growth of R. sphaeroides O.U 001 in the second stage. Modified Gompertz equation was applied to estimate the hydrogen production potential, rate and lag phase time in a batch process for various initial concentration of glucose, based on the cumulative hydrogen production curves. Both the curve fitting and statistical analysis showed that the equation was suitable to describe the progress of cumulative hydrogen production. (author)

  10. Mechanisms and kinetic profiles of superoxide-stimulated nitrosative processes in cells using a diaminofluorescein probe.

    Science.gov (United States)

    Damasceno, Fernando Cruvinel; Facci, Rômulo Rodrigues; da Silva, Thalita Marques; Toledo, José Carlos

    2014-12-01

    In this study, we examined the mechanisms and kinetic profiles of intracellular nitrosative processes using diaminofluorescein (DAF-2) as a target in RAW 264.7 cells. The intracellular formation of the fluorescent, nitrosated product diaminofluorescein triazol (DAFT) from both endogenous and exogenous nitric oxide (NO) was prevented by deoxygenation and by cell membrane-permeable superoxide (O2(-)) scavengers but not by extracellular bovine Cu,Zn-SOD. In addition, the DAFT formation rate decreased in the presence of cell membrane-permeable Mn porphyrins that are known to scavenge peroxynitrite (ONOO(-)) but was enhanced by HCO3(-)/CO2. Together, these results indicate that nitrosative processes in RAW 264.7 cells depend on endogenous intracellular O2(-) and are stimulated by ONOO(-)/CO2-derived radical oxidants. The N2O3 scavenger sodium azide (NaN3) only partially attenuated the DAFT formation rate and only with high NO (>120 nM), suggesting that DAFT formation occurs by nitrosation (azide-susceptible DAFT formation) and predominantly by oxidative nitrosylation (azide-resistant DAFT formation). Interestingly, the DAFT formation rate increased linearly with NO concentrations of up to 120-140 nM but thereafter underwent a sharp transition and became insensitive to NO. This behavior indicates the sudden exhaustion of an endogenous cell substrate that reacts rapidly with NO and induces nitrosative processes, consistent with the involvement of intracellular O2(-). On the other hand, intracellular DAFT formation stimulated by a fixed flux of xanthine oxidase-derived extracellular O2(-) that also occurs by nitrosation and oxidative nitrosylation increased, peaked, and then decreased with increasing NO, as previously observed. Thus, our findings complementarily show that intra- and extracellular O2(-)-dependent nitrosative processes occurring by the same chemical mechanisms do not necessarily depend on NO concentration and exhibit different unusual kinetic profiles with

  11. Degradation of clofibric acid in UV/chlorine disinfection process: kinetics, reactive species contribution and pathways.

    Science.gov (United States)

    Tang, Yuqing; Shi, Xueting; Liu, Yongze; Feng, Li; Zhang, Liqiu

    2018-02-01

    As a potential endocrine disruptor, clofibric acid (CA) was investigated in this study for its degradation kinetics and pathways in UV/chlorine process. The results showed that CA in both UV photolysis and UV/chlorine processes could be degraded via pseudo-first-order kinetics, while it almost could not be degraded in the dark chlorination process. The observed rate constant ( k obs ) in UV photolysis was 0.0078 min -1, and increased to 0.0107 min -1 combining with 0.1 mM chlorine. The k obs increased to 0.0447 min -1 with further increasing the chlorine dosage from 0.1 to 1.0 mM, and reached a plateau at higher dosage (greater than 1.0 mM). The higher k obs was obtained at acid solution rather than basic solution. Moreover, the calculated contributions of radical species to k obs indicated that the HO• contributed significantly to CA degradation in acidic conditions, while the reactive chlorine species and UV direct photolysis dominated in neutral and basic solution. The degradation of CA was slightly inhibited in the presence of [Formula: see text] (1 ∼ 50 mM), barely affected by the presence of Cl - (1 ∼ 200 mM) and greatly suppressed by humic acid (0 ∼ 5 mg l -1 ). Thirteen main degradation intermediates and three degradation pathways of CA were identified during UV/chlorine process.

  12. Spectroscopy, microscopy and theoretical study of NO adsorption on MoS2 and Co-Mo-S hydrotreating catalysts

    DEFF Research Database (Denmark)

    Topsøe, Nan-Yu; Tuxen, Anders Kyrme; Hinnemann, Berit

    2011-01-01

    nfrared (IR) spectroscopy using NO as a probe molecule has been one of the important methods for characterizing hydrotreating catalysts, since this technique provides information on the nature and quantity of active edge sites of these catalysts. However, due to the strong adsorption of NO, which......) calculations, we present new atomic-scale insight into the nature of NO adsorption on MoS2 and Co-Mo-S nanoclusters. The DFT calculations and STM experiments show that NO does not adsorb at fully sulfided MoS2 edges not containing hydrogen. However, typical sulfided catalysts will have hydrogen present...... NO as a probe molecule to obtain detailed atomic-scale information on hydrotreating catalysts and the origins of activity differences. (C) 2011 Published by Elsevier Inc....

  13. Study of kinetics of extraction of actinides in processes of reprocessing of nuclear fuels

    International Nuclear Information System (INIS)

    Lamotte, Claude

    1978-01-01

    This research thesis reports a bibliographical study on extraction kinetics. After some generalities on solvent-based extraction, and on the chemistry of actinides in solution, on the methods of kinetics study which are generally used and their mathematical treatments, the author compares the published results for the extraction kinetics of nitric acid, uranium VI, uranium IV, neptunium IV and plutonium IV [fr

  14. High-pressure processing of apple juice: kinetics of pectin methyl esterase inactivation.

    Science.gov (United States)

    Riahi, Esmaeil; Ramaswamy, Hosahalli S

    2003-01-01

    High-pressure (HP) inactivation kinetics of pectin methyl esterase (PME) in apple juice were evaluated. Commercial PME was dispensed in clarified apple juice, sealed in dual peel sterilizable plastic bags, and subjected to different high-pressure processing conditions (200-400 MPa, 0-180 min). Residual enzyme activity was determined by a titration method estimating the rate of free carboxyl group released by the enzyme acting on pectin substrate at pH 7.5 (30 degrees C). The effects of pressure level and pressure holding time on enzyme inactivation were significant (p < 0.05). PME from the microbial source was found to be more resistant (p < 0.05) to pressure inactivation than PME from the orange peel. Almost a full decimal reduction in the activity of commercial PME was achieved by HP treatment at 400 MPa for 25 min. Inactivation kinetics were evaluated on the basis of a dual effect model involving a pressure pulse effect and a first-order rate model, and the pressure sensitivity of rate constants was modeled by using the z-value concept.

  15. Kinetic Behavior of Exchange-Driven Growth with Catalyzed-Birth Processes

    Science.gov (United States)

    Wang, Hai-Feng; Lin, Zhen-Quan; Kong, Xiang-Mu

    2006-12-01

    Two catalyzed-birth models of n-species (n>=2) aggregates with exchange-driven growth processes are proposed and compared. In the first one, the exchange reaction occurs between any two aggregates Amk and Amj of the same species with the rate kernels Km(k,j) = Kmkj (m = 1,2,...,n, n>=2), and aggregates of An species catalyze a monomer-birth of Al species (l = 1,2,...,n-1) with the catalysis rate kernel Jl(k,j) = Jlkjυ. The kinetic behaviors are investigated by means of the mean-field theory. We find that the evolution behavior of aggregate-size distribution alk(t) of Al species depends crucially on the value of the catalysis rate parameter υ: (i) alk(t) obeys the conventional scaling law in the case of υ0. In the second model, the mechanism of monomer-birth of An-species catalyzed by Al species is added on the basis of the first model, that is, the aggregates of Al and An species catalyze each other to cause monomer-birth. The kinetic behaviors of Al and An species are found to fall into two categories for the different υ: (i) growth obeying conventional scaling form with υ0.

  16. Conversion of Oleum papaveris seminis oil into methyl esters via esterification process optimization and kinetic study

    Energy Technology Data Exchange (ETDEWEB)

    Syam, A.M.; Rashid, U.; Yunus, R.; Hamid, H.A.; Al-Resayes, S.I.; Nehdi, I.A.; Al-Muhtaseb, A.H.

    2016-07-01

    This paper presents an acid pre-treatment process and a kinetic study for the esterification reaction of Oleum papaveris seminis oil with methanol in the presence of amberlite 120 as a solid catalyst to convert the oil into methyl esters. Response surface methodology (RSM) was applied to optimize the reaction parameters, i.e. reaction time, percentage of the catalyst and volume ratio of methanol to oil. The results revealed that 0.87% w/w of catalyst concentration and 44.70% v/v of methanol to oil ratio provided final free fatty acid (FFA) contents of 0.60% w/w at 102.40 min of reaction time. It proved that the contribution of Amberlite 120 in the esterification of FFA was highly significant. The kinetics of the esterification in Oleum papaveris seminis oil with methanol in the presence of the amberlite 120 catalyst were also investigated to establish the reaction rate constant (k), reaction order, and activation energy. The study was performed under the optimized parameters at three reaction temperatures (50, 55, and 60 ºC). The value of k was in the range of 0.013 to 0.027 min-1. The first-order kinetics’ model was suitable for this irreversible FFA esterification with the activation energy of about 60.9 KJ·mol-1. (Author)

  17. Combined TGA-MS kinetic analysis of multistep processes. Thermal decomposition and ceramification of polysilazane and polysiloxane preceramic polymers.

    Science.gov (United States)

    García-Garrido, C; Sánchez-Jiménez, P E; Pérez-Maqueda, L A; Perejón, A; Criado, José M

    2016-10-26

    The polymer-to-ceramic transformation kinetics of two widely employed ceramic precursors, 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane (TTCS) and polyureamethylvinylsilazane (CERASET), have been investigated using coupled thermogravimetry and mass spectrometry (TG-MS), Raman, XRD and FTIR. The thermally induced decomposition of the pre-ceramic polymer is the critical step in the synthesis of polymer derived ceramics (PDCs) and accurate kinetic modeling is key to attaining a complete understanding of the underlying process and to attempt any behavior predictions. However, obtaining a precise kinetic description of processes of such complexity, consisting of several largely overlapping physico-chemical processes comprising the cleavage of the starting polymeric network and the release of organic moieties, is extremely difficult. Here, by using the evolved gases detected by MS as a guide it has been possible to determine the number of steps that compose the overall process, which was subsequently resolved using a semiempirical deconvolution method based on the Frasier-Suzuki function. Such a function is more appropriate that the more usual Gaussian or Lorentzian functions since it takes into account the intrinsic asymmetry of kinetic curves. Then, the kinetic parameters of each constituent step were independently determined using both model-free and model-fitting procedures, and it was found that the processes obey mostly diffusion models which can be attributed to the diffusion of the released gases through the solid matrix. The validity of the obtained kinetic parameters was tested not only by the successful reconstruction of the original experimental curves, but also by predicting the kinetic curves of the overall processes yielded by different thermal schedules and by a mixed TTCS-CERASET precursor.

  18. How Monte Carlo heuristics aid to identify the physical processes of drug release kinetics.

    Science.gov (United States)

    Lecca, Paola

    2018-01-01

    We implement a Monte Carlo heuristic algorithm to model drug release from a solid dosage form. We show that with Monte Carlo simulations it is possible to identify and explain the causes of the unsatisfactory predictive power of current drug release models. It is well known that the power-law, the exponential models, as well as those derived from or inspired by them accurately reproduce only the first 60% of the release curve of a drug from a dosage form. In this study, by using Monte Carlo simulation approaches, we show that these models fit quite accurately almost the entire release profile when the release kinetics is not governed by the coexistence of different physico-chemical mechanisms. We show that the accuracy of the traditional models are comparable with those of Monte Carlo heuristics when these heuristics approximate and oversimply the phenomenology of drug release. This observation suggests to develop and use novel Monte Carlo simulation heuristics able to describe the complexity of the release kinetics, and consequently to generate data more similar to those observed in real experiments. Implementing Monte Carlo simulation heuristics of the drug release phenomenology may be much straightforward and efficient than hypothesizing and implementing from scratch complex mathematical models of the physical processes involved in drug release. Identifying and understanding through simulation heuristics what processes of this phenomenology reproduce the observed data and then formalize them in mathematics may allow avoiding time-consuming, trial-error based regression procedures. Three bullet points, highlighting the customization of the procedure. •An efficient heuristics based on Monte Carlo methods for simulating drug release from solid dosage form encodes is presented. It specifies the model of the physical process in a simple but accurate way in the formula of the Monte Carlo Micro Step (MCS) time interval.•Given the experimentally observed curve of

  19. Rapid examination of the kinetic process of intramolecular lactamization of gabapentin using DSC-FTIR

    International Nuclear Information System (INIS)

    Hsu, C.-H.; Lin, S.-Y.

    2009-01-01

    The thermal stability and thermodynamics of gabapentin (GBP) in the solid state were investigated by DSC and TG techniques, and FTIR microspectroscopy. The detailed intramolecular lactamization process of GBP to form gabapentin-lactam (GBP-L) was also determined by thermal FTIR microspectroscopy. GBP exhibited a DSC endothermic peak at 169 deg. C. The weight loss in TG curve of GBP suggested that the evaporation process of water liberated via intramolecular lactamization was simultaneously combined with the evaporation process of GBP-L having a DSC endothermic peak at 91 deg. C. A thermal FTIR microspectroscopy clearly evidenced the IR spectra at 3350 cm -1 for water liberated and at 1701 cm -1 for lactam structure formed due to the lactam formation of GBP. This study indicates that the activation energy for combined processes of intramolecular lactamization of GBP and evaporation of GBP-L was about 114.3 ± 23.3 kJ/mol, but for the evaporation of GBP-L alone was 76.2 ± 1.5 kJ/mol. A powerful simultaneous DSC-FTIR combined technique was easily used to quickly examine the detailed kinetic processes of intramolecular cyclization of GPB and evaporation of GBP-L in the solid state

  20. Thermodynamics of information processing based on enzyme kinetics: An exactly solvable model of an information pump.

    Science.gov (United States)

    Cao, Yuansheng; Gong, Zongping; Quan, H T

    2015-06-01

    Motivated by the recent proposed models of the information engine [Proc. Natl. Acad. Sci. USA 109, 11641 (2012)] and the information refrigerator [Phys. Rev. Lett. 111, 030602 (2013)], we propose a minimal model of the information pump and the information eraser based on enzyme kinetics. This device can either pump molecules against the chemical potential gradient by consuming the information to be encoded in the bit stream or (partially) erase the information initially encoded in the bit stream by consuming the Gibbs free energy. The dynamics of this model is solved exactly, and the "phase diagram" of the operation regimes is determined. The efficiency and the power of the information machine is analyzed. The validity of the second law of thermodynamics within our model is clarified. Our model offers a simple paradigm for the investigating of the thermodynamics of information processing involving the chemical potential in small systems.

  1. Study of ferrallitisation process in soil by application of isotopic dilution kinetic technique to iron

    International Nuclear Information System (INIS)

    Thomann, Christiane

    1978-01-01

    Isotopic dilution kinetic technique applied to iron may contribute to make clear the conditions of ''potential'' mobility of iron in soils, under the action of three factors: moisture, incubation period and organic matter imputs. Comparison between surface horizons of three tropical soils: leached ferruginous tropical soil, weakly ferrallitic red soil and ferrallitic soil shows that in the ferrallitisation process, weakly ferrallitic soil would take place between the two other types of soils with a maximum mobility of iron. This mobility decreases when organic matter rate decreases leading then to ''beige'' soil (ferruginous leached tropical soil), and when hydroxide rate increases, which leads to ferrallitic soil. In podzol (A 1 horizon), for the same rate of organic matter, potential mobility of iron is higher than in ferallitic soil, because it contains ten times more free iron than the podzol [fr

  2. Kinetics and mechanism of azo dye destruction in advanced oxidation processes

    International Nuclear Information System (INIS)

    Wojnarovits, L.; Palfi, T.; Takacs, E.

    2007-01-01

    The kinetics and mechanism of dye destruction in advanced oxidation processes is discussed on the example of Apollofix Red (Ar-28) radiolysis in aqueous solution. When the reactive intermediate reacts with the color bearing part of the molecule causing with nearly 100% efficiency destruction of the conjugation, the dose dependence, or time dependence of color disappearance is linear. In this case, spectrophotometry can be used to follow-up dye decomposition. Linear dependence was observed when hydrated electrons or hydrogen atoms reacted with the dye. In hydroxyl radical reactions some colored products form with spectra similar to those of the starting dye molecules. For that reason, spectrophotometry gives false result about the intact dye molecule concentration. Analysis by the HPLC reveals logarithmic time dependence in agreement with a theoretical model developed

  3. Thermodynamics of information processing based on enzyme kinetics: An exactly solvable model of an information pump

    Science.gov (United States)

    Cao, Yuansheng; Gong, Zongping; Quan, H. T.

    2015-06-01

    Motivated by the recent proposed models of the information engine [Proc. Natl. Acad. Sci. USA 109, 11641 (2012), 10.1073/pnas.1204263109] and the information refrigerator [Phys. Rev. Lett. 111, 030602 (2013), 10.1103/PhysRevLett.111.030602], we propose a minimal model of the information pump and the information eraser based on enzyme kinetics. This device can either pump molecules against the chemical potential gradient by consuming the information to be encoded in the bit stream or (partially) erase the information initially encoded in the bit stream by consuming the Gibbs free energy. The dynamics of this model is solved exactly, and the "phase diagram" of the operation regimes is determined. The efficiency and the power of the information machine is analyzed. The validity of the second law of thermodynamics within our model is clarified. Our model offers a simple paradigm for the investigating of the thermodynamics of information processing involving the chemical potential in small systems.

  4. Kinetic theory of age-structured stochastic birth-death processes

    Science.gov (United States)

    Greenman, Chris D.; Chou, Tom

    2016-01-01

    Classical age-structured mass-action models such as the McKendrick-von Foerster equation have been extensively studied but are unable to describe stochastic fluctuations or population-size-dependent birth and death rates. Stochastic theories that treat semi-Markov age-dependent processes using, e.g., the Bellman-Harris equation do not resolve a population's age structure and are unable to quantify population-size dependencies. Conversely, current theories that include size-dependent population dynamics (e.g., mathematical models that include carrying capacity such as the logistic equation) cannot be easily extended to take into account age-dependent birth and death rates. In this paper, we present a systematic derivation of a new, fully stochastic kinetic theory for interacting age-structured populations. By defining multiparticle probability density functions, we derive a hierarchy of kinetic equations for the stochastic evolution of an aging population undergoing birth and death. We show that the fully stochastic age-dependent birth-death process precludes factorization of the corresponding probability densities, which then must be solved by using a Bogoliubov--Born--Green--Kirkwood--Yvon-like hierarchy. Explicit solutions are derived in three limits: no birth, no death, and steady state. These are then compared with their corresponding mean-field results. Our results generalize both deterministic models and existing master equation approaches by providing an intuitive and efficient way to simultaneously model age- and population-dependent stochastic dynamics applicable to the study of demography, stem cell dynamics, and disease evolution.

  5. Simultaneous saccharification and bioethanol production from corn cobs: Process optimization and kinetic studies.

    Science.gov (United States)

    Sewsynker-Sukai, Yeshona; Gueguim Kana, E B

    2018-08-01

    This study investigates the simultaneous saccharification and fermentation (SSF) process for bioethanol production from corn cobs with prehydrolysis (PSSF) and without prehydrolysis (OSSF). Two response surface models were developed with high coefficients of determination (>0.90). Process optimization gave high bioethanol concentrations and bioethanol conversions for the PSSF (36.92 ± 1.34 g/L and 62.36 ± 2.27%) and OSSF (35.04 ± 0.170 g/L and 58.13 ± 0.283%) models respectively. Additionally, the logistic and modified Gompertz models were used to study the kinetics of microbial cell growth and ethanol formation under microaerophilic and anaerobic conditions. Cell growth in the OSSF microaerophilic process gave the highest maximum specific growth rate (µ max ) of 0.274 h -1 . The PSSF microaerophilic bioprocess gave the highest potential maximum bioethanol concentration (P m ) (42.24 g/L). This study demonstrated that microaerophilic rather than anaerobic culture conditions enhanced cell growth and bioethanol production, and that additional prehydrolysis steps do not significantly impact on the bioethanol concentration and conversion in SSF process. Copyright © 2018 Elsevier Ltd. All rights reserved.

  6. Study on fermentation kinetics and extraction process of rhamnolipid production by papermaking wastewater

    Science.gov (United States)

    Yu, Keer

    2018-01-01

    Paper mill wastewater (PMW) is the outlet water generated during pulp and papermaking process in the paper industry. Fermentation by wastewater can lower the cost of production as well as alleviate the pressure of wastewater treatment. Rhamnolipids find broad placations as natural surfactants. This paper studied the rhamnolipids fermentation by employing Pseudomonas aeruginosa isolated by the laboratory, and determined to use wastewater which filtered by medium speed filter paper and strain Z2, the culture conditions were optimized, based on the flask shaking fermentation. On the basis of 5L tank fermentation, batch fermentation was carried out, the yield of fermentation reached 7.067g/L and the fermentation kinetics model of cell growth, product formation and substrate consumption was established by using origin software, and the fermentation process could be simulated well. And studied on the extraction process of rhamnolipids, through fermentation dynamic equation analysis can predict the in fill material yield can be further improved. Research on the extraction process of rhamnolipid simplifies the operation of extraction, and lays the foundation for the industrial extraction.

  7. Kinetics and efficiency of the hydrated electron-induced dehalogenation by the sulfite/UV process.

    Science.gov (United States)

    Li, Xuchun; Fang, Jingyun; Liu, Guifang; Zhang, Shujuan; Pan, Bingcai; Ma, Jun

    2014-10-01

    Hydrated electron (e(aq)(-)), which is listed among the most reactive reducing species, has great potential for removal and detoxification of recalcitrant contaminants. Here we provided quantitative insight into the availability and conversion of e(aq)(-) in a newly developed sulfite/UV process. Using monochloroacetic acid as a simple e(aq)(-)-probe, the e(aq)(-)-induced dehalogenation kinetics in synthetic and surface water was well predicted by the developed models. The models interpreted the complex roles of pH and S(IV), and also revealed the positive effects of UV intensity and temperature quantitatively. Impacts of humic acid, ferrous ion, carbonate/bicarbonate, and surface water matrix were also examined. Despite the retardation of dehalogenation by electron scavengers, the process was effective even in surface water. Efficiency of the process was discussed, and the optimization approaches were proposed. This study is believed to better understand the e(aq)(-)-induced dehalogenation by the sulfite/UV process in a quantitative manner, which is very important for its potential application in water treatment. Copyright © 2014 Elsevier Ltd. All rights reserved.

  8. Biogas Production from Sugarcane Waste: Assessment on Kinetic Challenges for Process Designing

    Science.gov (United States)

    Janke, Leandro; Leite, Athaydes; Nikolausz, Marcell; Schmidt, Thomas; Liebetrau, Jan; Nelles, Michael; Stinner, Walter

    2015-01-01

    Biogas production from sugarcane waste has large potential for energy generation, however, to enable the optimization of the anaerobic digestion (AD) process each substrate characteristic should be carefully evaluated. In this study, the kinetic challenges for biogas production from different types of sugarcane waste were assessed. Samples of vinasse, filter cake, bagasse, and straw were analyzed in terms of total and volatile solids, chemical oxygen demand, macronutrients, trace elements, and nutritional value. Biochemical methane potential assays were performed to evaluate the energy potential of the substrates according to different types of sugarcane plants. Methane yields varied considerably (5–181 Nm3·tonFM−1), mainly due to the different substrate characteristics and sugar and/or ethanol production processes. Therefore, for the optimization of AD on a large-scale, continuous stirred-tank reactor with long hydraulic retention times (>35 days) should be used for biogas production from bagasse and straw, coupled with pre-treatment process to enhance the degradation of the fibrous carbohydrates. Biomass immobilization systems are recommended in case vinasse is used as substrate, due to its low solid content, while filter cake could complement the biogas production from vinasse during the sugarcane offseason, providing a higher utilization of the biogas system during the entire year. PMID:26404248

  9. Simulation of the process kinetics and analysis of physicochemical properties in the freeze drying of kale

    Science.gov (United States)

    Dziki, Dariusz; Polak, Renata; Rudy, Stanisław; Krzykowski, Andrzej; Gawlik-Dziki, Urszula; Różyło, Renata; Miś, Antoni; Combrzyński, Maciej

    2018-01-01

    Investigations were performed to study the freeze-drying process of kale (Brassica oleracea L. var acephala). The process of freeze-drying was performed at temperatures of 20, 40, and 60°C for whole pieces of leaves and for pulped leaves. The kinetics of the freeze-drying of both kale leaves and kale pulp were best described by the Page model. The increasing freeze-drying temperature from 20 to 60°C induced an approximately two-fold decrease in the drying time. Freeze-drying significantly increased the value of the lightness, delta Chroma, and browning index of kale, and had little influence on the hue angle. The highest increase in the lightness and delta Chroma was observed for whole leaves freeze-dried at 20°C. An increase in the drying temperature brought about a slight decrease in the lightness, delta Chroma and the total colour difference. Pulping decreased the lightness and hue angle, and increased browning index. Freeze-drying engendered a slight decrease in the total phenolics content and antioxidant activity, in comparison to fresh leaves. The temperature of the process and pulping had little influence on the total phenolics content and antioxidant activity of dried kale, but significantly decreased the contents of chlorophyll a and chlorophyll b.

  10. Kinetic evaluation and process performance of a fixed film bioreactor removing phthalic acid and dimethyl phthalate.

    Science.gov (United States)

    Pirsaheb, Meghdad; Mesdaghinia, Ali-Reza; Shahtaheri, Seyed Jamaleddin; Zinatizadeh, Ali Akbar

    2009-08-15

    Phthalate esters are toxic organic contaminants which can enter into the environment through various industrial processes. In this study, a 6-liter fixed film bioreactor was used to examine biodegradation of phthalic acid (PA) and dimethyl phthalate (DMP) in synthetic wastewater. Effect on the process of two operating factors, namely hydraulic retention time (HRT) (at four levels ranging between 6 and 48 h) and initial phthalate concentrations (at six levels ranging from 10mg to 500 mg/l), was investigated. The process was stable at all operating conditions, except for the condition with influent PA and DMP of 500 mg/l and HRT of 6h. More than 95% removal efficiency was achieved for the conditions with HRT longer than 10h. Remarkable amount of DMP (398 mg/kg of sludge) was adsorbed on the biomass due to its higher hydrophobicity compared to PA (171 mg/kg). The kinetic parameters (mu(m,)K(s), Y and K(d)) were determined and compared for both substrates, PA and DMP.

  11. Kinetics Studies on the Process of Zn Removal from Wastewater Using Ultrasonically Activated Sorbents

    Directory of Open Access Journals (Sweden)

    R. Flores

    2017-04-01

    Full Text Available Heavy metals pollution in industrial wastewater is a great environmental challenge. Several techniques and materials have been recently proposed in order to overcome this problem, such as the adsorption process; however, in order to be competitive, new improved low-cost materials must be proposed or developed. In the present work, the remediation of Zn-contaminated water using fly ash and Tonsil was studied. Both materials are considered low-cost sorbents since they are a byproduct of an industrial process, or locally abundant in nature. To increase the Zn uptake, the materials were activated by applying ultrasonic energy. It was found that the pH is an important parameter to be controlled since the larger sorption capacity occurred at pH = 4. Also, the materials activated with ultrasound were able to adsorb greater Zn quantities at the studied experimental conditions. Finally, the kinetics of the adsorption process was analyzed, and several mathematical models were proposed to simulate the experimental data. After making some statistical discrimination, the Lagergren model was selected to represent the sorption of Zn on the different materials studied.

  12. Study on copper kinetics in processing sulphide ore mixed with copper and zinc with sulfuric acid leaching under pressure

    Science.gov (United States)

    Wen-bo, LUO; Ji-kun, WANG; Yin, GAN

    2018-01-01

    Sulphide ore mixed with copper and zinc is processed with pressure acid leaching. Research is conducted on the copper kinetic. The stirring rate is set at 600 rpm which could eliminate the influence of external diffusions. Research is conducted on the factors affecting the copper leaching kinetic are temperature, pressure, concentration of sulfuric acid, particle size. The result shows that the apparent activity energy is 50.7 KJ/mol. We could determine that the copper leaching process is shrinking core model of chemical reaction control and work out the leaching equation.

  13. On the problem of a consistent description of kinetic and hydrodynamic processes in dense gases and liquids

    Directory of Open Access Journals (Sweden)

    B.B. Markiv

    2010-01-01

    Full Text Available For a consistent description of kinetic and hydrodynamic processes in dense gases and liquids the generalized non-Markovian equations for the nonequilibrium one-particle distribution function and potential part of the averaged enthalpy density are obtained. The inner structure of the generalized transport kernels for these equations is established. It is shown that the collision integral of the kinetic equation has the Fokker-Planck form with the generalized friction coefficient in momentum space. It also contains contributions from the generalized diffusion coefficient and dissipative processes connected with the potential part of the enthalpy density.

  14. Kinetic Behavior of Exchange-Driven Growth with Catalyzed-Birth Processes

    International Nuclear Information System (INIS)

    Wang Haifeng; Lin Zhenquan; Kong Xiangmu

    2006-01-01

    Two catalyzed-birth models of n-species (n≥2) aggregates with exchange-driven growth processes are proposed and compared. In the first one, the exchange reaction occurs between any two aggregates A m k and A m j of the same species with the rate kernels K m (k,j) = K m kj (m = 1,2,...,n, n≥2), and aggregates of A n species catalyze a monomer-birth of A l species (l = 1,2,...,n-1) with the catalysis rate kernel J l (k,j) = J l kj υ . The kinetic behaviors are investigated by means of the mean-field theory. We find that the evolution behavior of aggregate-size distribution a l k (t) of A l species depends crucially on the value of the catalysis rate parameter υ: (i) a l k (t) obeys the conventional scaling law in the case of υ≤0, (ii) a l k (t) satisfies a modified scaling form in the case of υ>0. In the second model, the mechanism of monomer-birth of A n -species catalyzed by A l species is added on the basis of the first model, that is, the aggregates of A l and A n species catalyze each other to cause monomer-birth. The kinetic behaviors of A l and A n species are found to fall into two categories for the different υ: (i) growth obeying conventional scaling form with υ≤0, (ii) gelling at finite time with υ>0.

  15. Hydrotreating of compounds and mixtures of compounds having mercapto and hydroxyl groups

    Energy Technology Data Exchange (ETDEWEB)

    Viljava, T.R.; Krause, A.O.I. [Helsinki University of Technology, Espoo (Finland)

    1997-07-01

    Simultaneous hydrodesulfurization (HDS) and hydrodeoxygenation (HDO) of mercapto and hydroxyl group containing benzenes was studied using a commercial presulfided CoMo/{gamma}- Al{sub 2}O{sub 3} catalyst under hydrotreating conditions (150-280 deg C, 7 MPa). Mercaptobenzene, phenol and 4-mercaptophenol were used as model compounds, and CS{sub 2} was used as precursor for H{sub 2}S. The HDS rate of a mercapto group in the presence of a hydroxyl substituent in the para position was higher than that for the molecule containing only a mercapto group. When the hydroxyl group was present as phenol, the HDS rate of the mercapto group was about 30% lower than that for mercaptobenzene without an oxygen-containing additive. The decrease in the HDS rate was independent of the initial molar ratio of sulfur and oxygen within the ratios studied (5:1-1:1). The HDO rate of a hydroxyl group was suppressed by the mercapto group present either in the same or in a separate molecule. HDO reactions did not start until HDS conversion was almost complete. CS{sub 2} also decreased the HDO rate of phenol. When compared to the reactions of phenol alone, the rate of the hydrogenolysis route to benzene was decreased in the presence of a sulfur additive more than the hydrogenolysis- hydrogenation route to cyclohexane. 19 refs.

  16. Environmental Impacts and Costs of Hydrotreated Vegetable Oils, Transesterified Lipids and Woody BTL—A Review

    Directory of Open Access Journals (Sweden)

    Andreas Brekke

    2011-05-01

    Full Text Available This article reviews and compares assessments of three biodiesel fuels: (1 transesterified lipids, (2 hydrotreated vegetable oils (HVO, and (3 woody biomass-to-liquid (BTL Fischer-Tropsch diesel and selected feedstock options. The article attempts to rank the environmental performance and costs of fuel and feedstock combinations. Due to inter-study differences in goal and study assumptions, the ranking was mostly qualitative and intra-study results are emphasized. Results indicate that HVO made from wastes or by-products such as tall oil, tallow or used cooking oil outperform transesterified lipids and BTL from woody material, both with respect to environmental life cycle impacts and costs. These feedstock options are, however, of limited availability, and to produce larger volumes of biofuels other raw materials must also be used. BTL from woody biomass seems promising with good environmental performance and the ability not to compete with food production. Production of biofuels from agricultural feedstock sources requires much energy and leads to considerable emissions due to agrochemical inputs. Thus, such biodiesel fuels are ranked lowest in this comparison. Production of feedstock is the most important life cycle stage. Avoiding detrimental land use changes and maintaining good agricultural or forestry management practices are the main challenges to ensure that biofuels can be a sustainable option for the future transport sector.

  17. Heterocatalytic Fenton oxidation process for the treatment of tannery effluent: kinetic and thermodynamic studies.

    Science.gov (United States)

    Karthikeyan, S; Ezhil Priya, M; Boopathy, R; Velan, M; Mandal, A B; Sekaran, G

    2012-06-01

    BACKGROUND, AIM, SCOPE: Treatment of wastewater has become significant with the declining water resources. The presence of recalcitrant organics is the major issue in meeting the pollution control board norms in India. The theme of the present investigation was on partial or complete removal of pollutants or their transformation into less toxic and more biodegradable products by heterogeneous Fenton oxidation process using mesoporous activated carbon (MAC) as the catalyst. Ferrous sulfate (FeSO(4)·7H(2)O), sulfuric acid (36 N, specific gravity 1.81, 98% purity), hydrogen peroxide (50% v/v) and all other chemicals used in this study were of analytical grade (Merck). Two reactors, each of height 50 cm and diameter 6 cm, were fabricated with PVC while one reactor was packed with MAC of mass 150 g and other without MAC served as control. The oxidation process was presented with kinetic and thermodynamic constants for the removal of COD, BOD, and TOC from the wastewater. The activation energy (Ea) for homogeneous and heterogeneous Fenton oxidation processes were 44.79 and 25.89 kJ/mol, respectively. The thermodynamic parameters ΔG, ΔH, and ΔS were calculated for the oxidation processes using Van't Hoff equation. Furthermore, the degradation of organics was confirmed through FTIR and UV-visible spectroscopy, and cyclic voltammetry. The heterocatalytic Fenton oxidation process efficiently increased the biodegradability index (BOD/COD) of the tannery effluent. The optimized conditions for the heterocatalytic Fenton oxidation of organics in tannery effluent were pH 3.5, reaction time-4 h, and H(2)O(2)/FeSO(4)·7H(2)O in the molar ratio of 2:1.

  18. First principle chemical kinetics in zeolites: the methanol-to-olefin process as a case study.

    Science.gov (United States)

    Van Speybroeck, Veronique; De Wispelaere, Kristof; Van der Mynsbrugge, Jeroen; Vandichel, Matthias; Hemelsoet, Karen; Waroquier, Michel

    2014-11-07

    To optimally design next generation catalysts a thorough understanding of the chemical phenomena at the molecular scale is a prerequisite. Apart from qualitative knowledge on the reaction mechanism, it is also essential to be able to predict accurate rate constants. Molecular modeling has become a ubiquitous tool within the field of heterogeneous catalysis. Herein, we review current computational procedures to determine chemical kinetics from first principles, thus by using no experimental input and by modeling the catalyst and reacting species at the molecular level. Therefore, we use the methanol-to-olefin (MTO) process as a case study to illustrate the various theoretical concepts. This process is a showcase example where rational design of the catalyst was for a long time performed on the basis of trial and error, due to insufficient knowledge of the mechanism. For theoreticians the MTO process is particularly challenging as the catalyst has an inherent supramolecular nature, for which not only the Brønsted acidic site is important but also organic species, trapped in the zeolite pores, must be essentially present during active catalyst operation. All these aspects give rise to specific challenges for theoretical modeling. It is shown that present computational techniques have matured to a level where accurate enthalpy barriers and rate constants can be predicted for reactions occurring at a single active site. The comparison with experimental data such as apparent kinetic data for well-defined elementary reactions has become feasible as current computational techniques also allow predicting adsorption enthalpies with reasonable accuracy. Real catalysts are truly heterogeneous in a space- and time-like manner. Future theory developments should focus on extending our view towards phenomena occurring at longer length and time scales and integrating information from various scales towards a unified understanding of the catalyst. Within this respect molecular

  19. Analysis of exergy loss of gasoline surrogate combustion process based on detailed chemical kinetics

    International Nuclear Information System (INIS)

    Sun, Hongjie; Yan, Feng; Yu, Hao; Su, W.H.

    2015-01-01

    Highlights: • We explored the exergy loss sources of gasoline engine like combustion process. • The model combined non-equilibrium thermodynamics with detailed chemical kinetics. • We explored effects of initial conditions on exergy loss of combustion process. • Exergy loss decreases 15% of fuel chemical exergy by design of initial conditions. • Correspondingly, the second law efficiency increases from 38.9% to 68.9%. - Abstract: Chemical reaction is the most important source of combustion irreversibility in premixed conditions, but details of the exergy loss mechanisms have not been explored yet. In this study numerical analysis based on non-equilibrium thermodynamics combined with detailed chemical kinetics is conducted to explore the exergy loss mechanism of gasoline engine like combustion process which is simplified as constant volume combustion. The fuel is represented by the common accepted gasoline surrogates which consist of four components: iso-octane (57%), n-heptane (16%), toluene (23%), and 2-pentene (4%). We find that overall exergy loss is mainly composed of three peaks along combustion generated from chemical reactions in three stages, the conversion from large fuel molecules into small molecules (as Stage 1), the H 2 O 2 loop-related reactions (as Stage 2), and the violent oxidation reactions of CO, H, and O (as Stage 3). The effects of individual combustion boundaries, including temperature, pressure, equivalence ratio, oxygen concentration, on combustion exergy loss have been widely investigated. The combined effects of combustion boundaries on the total loss of gasoline surrogates are also investigated. We find that in a gasoline engine with a compression ratio of 10, the total loss can be reduced from 31.3% to 24.3% using lean combustion. The total loss can be further reduced to 22.4% by introducing exhaust gas recirculation and boosting the inlet charge. If the compression ratio is increased to 17, the total loss can be decreased to

  20. Application of a hybrid Electrocoagulation-Fenton process in yarn dye wastewater: Kinetic study

    Science.gov (United States)

    Riadi, L.; Sapei, L.; Lidiawati, T.; Agustin, Y. E.

    2016-11-01

    Reactive dyes contain a significant portion of colorants used in yarn dying process and also in textile industry. Since the COD content is usually high in such wastewater,we conducted a hybrid electrocoagulation-fenton method to treat the wastewater. This work describes the application of the hybrid system to the removal of chemical oxygen demand and color from the wastewater in a batch reactor. Having worked with initial pH of 3,0; temperature at 30°C, molar ratio of Fe2+/H2O2 =1/10 and the mol ratio H2O2/COD = 4, we got 88.3% COD conversion and 88.5% color removal. The COD degradation process can be explained in two phases, the first phase is instantaneous reaction and the second phase is first order reaction. The kinetic constant was 0.0053 minute-1 and the rate of COD degradation was 0.0053[COD] mg/L minute.

  1. Kinetic study of thermophilic anaerobic digestion of solid wastes from potato processing

    International Nuclear Information System (INIS)

    Linke, Bernd

    2006-01-01

    Anaerobic treatment of solid wastes from potato processing was studied in completely stirred tank reactors (CSTR) at 55 o C. Special attention was paid to the effect of increased organic loading rate (OLR) on the biogas yield in long-term experiments. Both biogas yield and CH 4 in the biogas decreased with the increase in OLR. For OLR in the range of 0.8 gl -1 d -1 -3.4 gl -1 d -1 , biogas yield and CH 4 obtained were 0.85 l g -1 -0.65 l g -1 and 58%-50%, respectively. Biogas yield y as a function of maximum biogas yield y m , reaction rate constant k and HRT are described on the basis of a mass balance in a CSTR and a first order kinetic. The value of y m can be obtained from curve fitting or a simple batch test and k results from plotting y/(y m -y) against 1/OLR from long-term experiments. In the present study values for y m and k were obtained as 0.88 l g -1 and 0.089 d -1 , respectively. The simple model equations can apply for dimensioning completely stirred tank reactors (CSTR) digesting organic wastes from food processing industries, animal waste slurries or biogas crops

  2. Peroxone mineralization of chemical oxygen demand for direct potable water reuse: Kinetics and process control.

    Science.gov (United States)

    Wu, Tingting; Englehardt, James D

    2015-04-15

    Mineralization of organics in secondary effluent by the peroxone process was studied at a direct potable water reuse research treatment system serving an occupied four-bedroom, four bath university residence hall apartment. Organic concentrations were measured as chemical oxygen demand (COD) and kinetic runs were monitored at varying O3/H2O2 dosages and ratios. COD degradation could be accurately described as the parallel pseudo-1st order decay of rapidly and slowly-oxidizable fractions, and effluent COD was reduced to below the detection limit (<0.7 mg/L). At dosages ≥4.6 mg L(-1) h(-1), an O3/H2O2 mass ratio of 3.4-3.8, and initial COD <20 mg/L, a simple first order decay was indicated for both single-passed treated wastewater and recycled mineral water, and a relationship is proposed and demonstrated to estimate the pseudo-first order rate constant for design purposes. At this O3/H2O2 mass ratio, ORP and dissolved ozone were found to be useful process control indicators for monitoring COD mineralization in secondary effluent. Moreover, an average second order rate constant for OH oxidation of secondary effluent organics (measured as MCOD) was found to be 1.24 × 10(7) ± 0.64 × 10(7) M(-1) S(-1). The electric energy demand of the peroxone process is estimated at 1.73-2.49 kW h electric energy for removal of one log COD in 1 m(3) secondary effluent, comparable to the energy required for desalination of medium strength seawater. Advantages/disadvantages of the two processes for municipal wastewater reuse are discussed. Copyright © 2015 Elsevier Ltd. All rights reserved.

  3. Analysis of the kinetics of the fragile fracture process in Mo monocrystals in quasi-relaxation

    International Nuclear Information System (INIS)

    Tamayo Meza, Pedro; Bautista Godinez, Eric Gustavo; Yermishkin, Viacheslav

    2008-01-01

    The method of quasi-relaxation, generally known as the force relaxation method, has been widely applied in the study of elementary dislocational processes. It is essential for the study and analysis of thermoactivated mechanisms, for the determination of the energy of interaction between dislocations and inclusions, in the definition of the dislocational constants, to predict the development of creep, and even for the study of fracture kinetics. For the first time the use of the quasi-relaxation method for evaluating the fragile fracture tendency was presented in the work. However, as usually carried out, the use of mass specimens and the development of a considerable plastic deformation in the vertex of the crack-notch sample limits the possibilities for this method. Many studies analyze the theoretical aspects of the fracture process, and the obtention of reliable quantitative information about the behavior of the dislocation based on an analytical description of the process, and how and when it influences the conditions under which the final catastrophic fracture occurs. This work proposes a new method to analyze the effect of a tension concentrator on the surface of Mo monocrystal specimens. The relaxation of the force and the increase in the crack opening is related to the development of the plastic zone in its vertex with the help of the Irwin correction. During the relaxation, the crack-groove grows until it attains the length of the plastic zone. Specimens with and without force concentrators were tested in quasi-relaxation. The cracks appearing under these conditions are analyzed using a scanning electron microscopy (SEM). The crack appearing in the specimens under load conditions, whose development produced heavy force relaxation, allowed the force relaxation value to be defined and compared in the specimens with and without tension concentrators (au)

  4. Fiber Bragg Grating Sensor to Monitor Stress Kinetics in Drying Process of Commercial Latex Paints

    Directory of Open Access Journals (Sweden)

    Ivo de Lourenço

    2010-05-01

    Full Text Available In this paper, we report a study about the application of packaged fiber Bragg gratings used as strain sensors to monitor the stress kinetics during the drying process of commercial latex paints. Three stages of drying with distinct mechanical deformation and temporal behaviors were identified for the samples, with mechanical deformation from 15 μm to 21 μm in the longitudinal film dimension on time intervals from 370 to 600 minutes. Drying time tests based on human sense technique described by the Brazilian Technical Standards NBR 9558 were also done. The results obtained shows that human sense technique has a limited perception of the drying process and that the optical measurement system proposed can be used to characterize correctly the dry-through stage of paint. The influence of solvent (water addition in the drying process was also investigated. The paint was diluted with four parts paint and one part water (80% paint, and one part paint and one part water (50% paint. It was observed that the increase of the water ratio mixed into the paint decreases both the mechanical deformation magnitude and the paint dry-through time. Contraction of 5.2 μm and 10.4 μm were measured for concentrations of 50% and 80% of paint in the mixture, respectively. For both diluted paints the dry-through time was approximately 170 minutes less than undiluted paint. The optical technique proposed in this work can contribute to the development of new standards to specify the drying time of paint coatings.

  5. Developments in hydroconversion processes for residues

    Energy Technology Data Exchange (ETDEWEB)

    Douwes, C T [Shell Res. B.V.; Wijffels, J B; Van Klinken, J; Van Zijll Langhout, W C

    1979-01-01

    A review of recent developments in hydrotreating processes for demetallization, desulfurization, and conversion to distillate products of residues covers catalyst developments for suppression of coke formation, maximum metals tolerance, and conversion selectivity; the effects of hydrogen pressure and temperature on catalyst deactivation and conversion; basic operating characteristics of conventional fixed-bed trickle-flow reactors, and of onstream catalyst replacement reactors, including the expanded-bed and the moving-bed reactor; a comparison of catalyst bed activity level, dirt tolerance, reactor effectiveness, temperature control, and thermal stability of the expanded-bed and moving-bed reactors; residue upgrading in slurry-bed reactors of dispersed vanadium sulfide catalyst in the oil; design and control features for safety and reliability; and a cost comparison between the indirect hydrotreating route, in which the asphalt fraction is separated prior to hydrotreating, and the as yet incompletely developed direct route.

  6. 2D Numerical Modelling of the Resin Injection Pultrusion Process Including Experimental Resin Kinetics and Temperature Validation

    DEFF Research Database (Denmark)

    Rasmussen, Filip Salling; Sonne, Mads Rostgaard; Larsen, Martin

    In the present study, a two-dimensional (2D) transient Eulerian thermo-chemical analysis of a carbon fibre epoxy thermosetting Resin Injection Pultrusion (RIP) process is carried out. The numerical model is implemented using the well known unconditionally stable Alternating Direction Implicit (ADI......) scheme. The total heat of reaction and the cure kinetics of the epoxy thermosetting are determined using Differential Scanning Calorimetry (DSC). A very good agreement is observed between the fitted cure kinetic model and the experimental measurements. The numerical steady state temperature predictions...

  7. Kinetic parameters of biomass growth in a UASB reactor treating wastewater from coffee wet processing (WCWP

    Directory of Open Access Journals (Sweden)

    Claudio Milton Montenegro Campos

    2014-10-01

    Full Text Available This study evaluated the treatment of wastewater from coffee wet processing (WCWP in an anaerobic treatment system at a laboratory scale. The system included an acidification/equalization tank (AET, a heat exchanger, an Upflow Anaerobic Sludge Blanket Reactor (UASB, a gas equalization device and a gas meter. The minimum and maximum flow rates and volumetric organic loadings rate (VOLR were 0.004 to 0.037 m 3 d -1 and 0.14 to 20.29 kgCOD m -3 d -1 , respectively. The kinetic parameters measured during the anaerobic biodegradation of the WCWP, with a minimal concentration of phenolic compounds of 50 mg L - ¹, were: Y = 0.37 mgTVS (mgCODremoved -1 , Kd = 0.0075 d-1 , Ks = 1.504mg L -1 , μmax = 0.2 d -1 . The profile of sludge in the reactor showed total solids (TS values from 22,296 to 55,895 mg L -1 and TVS 11,853 to 41,509 mg L -1 , demonstrating a gradual increase of biomass in the reactor during the treatment, even in the presence of phenolic compounds in the concentration already mentioned.

  8. Atomistic Kinetic Monte Carlo studies of microchemical evolutions driven by diffusion processes under irradiation

    Science.gov (United States)

    Soisson, F.; Becquart, C. S.; Castin, N.; Domain, C.; Malerba, L.; Vincent, E.

    2010-11-01

    Atomistic Kinetic Monte Carlo (AKMC) simulations are a powerful tool to study the microstructural and microchemical evolution of alloys controlled by diffusion processes, under irradiation and during thermal ageing. In the framework of the FP6 Perfect program, two main approaches have been applied to binary and multicomponent iron based alloys. The first one is based on a diffusion model which takes into account vacancy and self-interstitial jumps, using simple rigid lattice approximation and broken-bond models to compute the point-defect jump frequencies. The corresponding parameters are fitted on ab initio calculations of a few typical configurations and migration barriers. The second method uses empirical potentials to compute a much larger number of migration barriers, including atomic relaxations, and Artificial Intelligence regression methods to predict the other ones. It is somewhat less rapid than the first one, but significantly more than simulations using "on-the-fly" calculations of all the barriers. We review here the recent advances and perspectives concerning these techniques.

  9. Atomistic Kinetic Monte Carlo studies of microchemical evolutions driven by diffusion processes under irradiation

    International Nuclear Information System (INIS)

    Soisson, F.; Becquart, C.S.; Castin, N.; Domain, C.; Malerba, L.; Vincent, E.

    2010-01-01

    Atomistic Kinetic Monte Carlo (AKMC) simulations are a powerful tool to study the microstructural and microchemical evolution of alloys controlled by diffusion processes, under irradiation and during thermal ageing. In the framework of the FP6 Perfect program, two main approaches have been applied to binary and multicomponent iron based alloys. The first one is based on a diffusion model which takes into account vacancy and self-interstitial jumps, using simple rigid lattice approximation and broken-bond models to compute the point-defect jump frequencies. The corresponding parameters are fitted on ab initio calculations of a few typical configurations and migration barriers. The second method uses empirical potentials to compute a much larger number of migration barriers, including atomic relaxations, and Artificial Intelligence regression methods to predict the other ones. It is somewhat less rapid than the first one, but significantly more than simulations using 'on-the-fly' calculations of all the barriers. We review here the recent advances and perspectives concerning these techniques.

  10. Degradation of diclofenac by UV-activated persulfate process: Kinetic studies, degradation pathways and toxicity assessments.

    Science.gov (United States)

    Lu, Xian; Shao, Yisheng; Gao, Naiyun; Chen, Juxiang; Zhang, Yansen; Xiang, Huiming; Guo, Youluo

    2017-07-01

    Diclofenac (DCF) is the frequently detected non-steroidal pharmaceuticals in the aquatic environment. In this study, the degradation of DCF was evaluated by UV-254nm activated persulfate (UV/PS). The degradation of DCF followed the pseudo first-order kinetics pattern. The degradation rate constant (k obs ) was accelerated by UV/PS compared to UV alone and PS alone. Increasing the initial PS dosage or solution pH significantly enhanced the degradation efficiency. Presence of various natural water constituents had different effects on DCF degradation, with an enhancement or inhibition in the presence of inorganic anions (HCO 3 - or Cl - ) and a significant inhibition in the presence of NOM. In addition, preliminary degradation mechanisms and major products were elucidated using LC-MS/MS. Hydroxylation, decarbonylation, ring-opening and cyclation reaction involving the attack of SO 4 • - or other substances, were the main degradation mechanism. TOC analyzer and Microtox bioassay were employed to evaluate the mineralization and cytotoxicity of solutions treated by UV/PS at different times, respectively. Limited elimination of TOC (32%) was observed during the mineralization of DCF. More toxic degradation products and their related intermediate species were formed, and the UV/PS process was suitable for removing the toxicity. Of note, longer degradation time may be considered for the final toxicity removal. Copyright © 2017. Published by Elsevier Inc.

  11. Theoretical Investigation of Kinetic Processes in Small Radicals of Importance in Combustion

    Energy Technology Data Exchange (ETDEWEB)

    Alexander, Millard [Univ. of Maryland, College Park, MD (United States). Dept. of Chemistry and Biochemistry; Dagdigian, Paul J. [Johns Hopkins Univ., Baltimore, MD (United States). Dept. of Chemistry

    2017-12-12

    Our group studies inelastic and reactive collisions of small molecules, focusing on radicals important in combustion environments. The goal is the better understanding of kinetic processes that may be difficult to access experimentally. An essential component is the accurate determination and fitting of potential energy surfaces (PESs). After fitting the ab initio points to obtain global PESs, we treat the dynamics using time-independent (close-coupling) methods. Cross sections and rate constants for collisions of are determined with our Hibridon program suite . We have studied energy transfer (rotationally, vibrationally, and/or electronically inelastic) in small hydrocarbon radicals (CH2 and CH3) and the CN radical. We have made a comparison with experimental measurements of relevant rate constants for collisions of these radicals. Also, we have calculated accurate transport properties using state-of-the-art PESs and to investigate the sensitivity to these parameters in 1-dimensional flame simulations. Of particular interest are collision pairs involving the light H atom.

  12. Hydrometallurgical Process and Kinetics of Leaching Manganese from Semi-Oxidized Manganese Ores with Sucrose

    Directory of Open Access Journals (Sweden)

    Yuhong Wang

    2017-02-01

    Full Text Available The extraction of manganese from a semi-oxidized manganese ore was investigated with sucrose as the reducing agent in dilute sulfuric acid medium. The kinetics of leaching manganese from the complex ore containing MnCO3 and MnO2 was also investigated. The effects of sucrose and sulfuric acid concentrations, leaching temperature and reaction time on the total Mn (TMn, MnO2 and MnCO3 leaching were investigated. Results showed that MnCO3 could more easily react with hydrogen ions than MnO2 in ores, and MnO2 decomposition could be advantageous for MnCO3 leaching. The leaching efficiencies of 91.8% for total Mn, 91.4% for MnO2 and 96.9% for MnCO3 were obtained under the following optimized conditions: 0.035 mol/L sucrose concentration, 5 mol/L sulfuric acid concentration, 60 min of reaction time and 363.2 K of leaching temperature. In addition, it was found that the leaching process of semi-oxidized manganese ore follows the shrinking core model and the leaching rate was controlled by chemical reaction and diffusion. The apparent activation energy of the total manganese, MnO2, and MnCO3 leaching were 40.83, 40.59, and 53.33 kJ·mol−1, respectively.

  13. Arabidopsis peroxidase-catalyzed copolymerization of coniferyl and sinapyl alcohols: kinetics of an endwise process.

    Science.gov (United States)

    Demont-Caulet, Nathalie; Lapierre, Catherine; Jouanin, Lise; Baumberger, Stéphanie; Méchin, Valérie

    2010-10-01

    In order to determine the mechanism of the earlier copolymerization steps of two main lignin precursors, sinapyl (S) alcohol and coniferyl (G) alcohol, microscale in vitro oxidations were carried out with a PRX34 Arabidopsis thaliana peroxidase in the presence of H(2)O(2). This plant peroxidase was found to have an in vitro polymerization activity similar to the commonly used horseradish peroxidase. The selected polymerization conditions lead to a bulk polymerization mechanism when G alcohol was the only phenolic substrate available. In the same conditions, the presence of S alcohol at a 50/50 S/G molar ratio turned this bulk mechanism into an endwise one. A kinetics monitoring (size-exclusion chromatography and liquid chromatography-mass spectrometry) of the different species formed during the first 24h oxidation of the S/G mixture allowed sequencing the bondings responsible for oligomerization. Whereas G homodimers and GS heterodimers exhibit low reactivity, the SS pinoresinol structure act as a nucleating site of the polymerization through an endwise process. This study is particularly relevant to understand the impact of S units on lignin structure in plants and to identify the key step at which this structure is programmed. Copyright © 2010 Elsevier Ltd. All rights reserved.

  14. Estimation of fundamental kinetic parameters of polyhydroxybutyrate fermentation process of Azohydromonas australica using statistical approach of media optimization.

    Science.gov (United States)

    Gahlawat, Geeta; Srivastava, Ashok K

    2012-11-01

    Polyhydroxybutyrate or PHB is a biodegradable and biocompatible thermoplastic with many interesting applications in medicine, food packaging, and tissue engineering materials. The present study deals with the enhanced production of PHB by Azohydromonas australica using sucrose and the estimation of fundamental kinetic parameters of PHB fermentation process. The preliminary culture growth inhibition studies were followed by statistical optimization of medium recipe using response surface methodology to increase the PHB production. Later on batch cultivation in a 7-L bioreactor was attempted using optimum concentration of medium components (process variables) obtained from statistical design to identify the batch growth and product kinetics parameters of PHB fermentation. A. australica exhibited a maximum biomass and PHB concentration of 8.71 and 6.24 g/L, respectively in bioreactor with an overall PHB production rate of 0.75 g/h. Bioreactor cultivation studies demonstrated that the specific biomass and PHB yield on sucrose was 0.37 and 0.29 g/g, respectively. The kinetic parameters obtained in the present investigation would be used in the development of a batch kinetic mathematical model for PHB production which will serve as launching pad for further process optimization studies, e.g., design of several bioreactor cultivation strategies to further enhance the biopolymer production.

  15. PENGARUH PERBEDAAN SIFAT PENYANGGA ALUMINA TERHADAP SIFAT KATALIS HYDROTREATING BERBASIS NIKEL-MOLIBDENUM

    Directory of Open Access Journals (Sweden)

    Maria Ulfah

    2012-11-01

    Full Text Available EFFECT OF ALUMINA SUPPORT PROPERTIES ON THE NICKEL-MOLIBDENUM BASE HYDROTREATING CATALYST. Effect of surface characteristics of three species of synthesized γ-alumina (alumina-1, alumina-2 and alumina-3 on characteristics NiMo catalysts has been studied. Those aluminas are derived from boehmite Catapal B by varying rasio mol nitric acid to boehmite. A sol-gel method is used to synthesize γ-Al2O3 support. The Nitrogen adsorption, X-ray diffraction (XRD, Temperature Programmed Reduction (TPR of H2, Temperature Programmed Desorption (TPD of NH3, and mechanical strength are used to characterize the supports and catalysts. The results showed that the surface area alumina affects the formation of crystalline MoO3 in the NiMo catalyst, while γ-Al2O3-3 support which has the highest surface area (about 195 m2/g compared to the other two types of alumina (>195 m2/g does not have a crystalline MoO3. The formation of crystalline MoO3 is not influenced by the acidity alumina. Based on the results of XRD, it is  indicated that the supported alumina-3 NiMo catalyst (having the highest acid strength shows that there is no presence of crystalline MoO3. Pore size distribution of support did not change significantly after the deposition of Ni and Mo oxides. Mechanical strength of support also affects the strength NiMo catalyst. Support alumina-3 which has the highest mechanical strength gives the mechanical strength of the highest NiMo catalyst. Pengaruh sifat penyangga γ-alumina hasil pengembangan (alumina-1, alumina-2 dan alumina-3 pada karakter katalis hydrotreating nikel-molibdenum (NiMo telah dipelajari. Ketiga jenis γ-alumina diturunkan dari boehmite “Catapal B” dengan menvariasikan nisbah mol asam nitrat terhadap boehmite. Pembuatan γ-alumina menggunakan metoda sol-gel. Adsorpsi Nitrogen, X-ray difraksi (XRD, Temperature Programmed Reduction (TPR H2, Temperature Programmed Desorption (TPD NH3, dan kekuatan mekanik digunakan untuk

  16. Automated analysis of information processing, kinetic independence and modular architecture in biochemical networks using MIDIA.

    Science.gov (United States)

    Bowsher, Clive G

    2011-02-15

    Understanding the encoding and propagation of information by biochemical reaction networks and the relationship of such information processing properties to modular network structure is of fundamental importance in the study of cell signalling and regulation. However, a rigorous, automated approach for general biochemical networks has not been available, and high-throughput analysis has therefore been out of reach. Modularization Identification by Dynamic Independence Algorithms (MIDIA) is a user-friendly, extensible R package that performs automated analysis of how information is processed by biochemical networks. An important component is the algorithm's ability to identify exact network decompositions based on both the mass action kinetics and informational properties of the network. These modularizations are visualized using a tree structure from which important dynamic conditional independence properties can be directly read. Only partial stoichiometric information needs to be used as input to MIDIA, and neither simulations nor knowledge of rate parameters are required. When applied to a signalling network, for example, the method identifies the routes and species involved in the sequential propagation of information between its multiple inputs and outputs. These routes correspond to the relevant paths in the tree structure and may be further visualized using the Input-Output Path Matrix tool. MIDIA remains computationally feasible for the largest network reconstructions currently available and is straightforward to use with models written in Systems Biology Markup Language (SBML). The package is distributed under the GNU General Public License and is available, together with a link to browsable Supplementary Material, at http://code.google.com/p/midia. Further information is at www.maths.bris.ac.uk/~macgb/Software.html.

  17. Adsorption of aluminum and lead from wastewater by chitosan-tannic acid modified biopolymers: Isotherms, kinetics, thermodynamics and process mechanism.

    Science.gov (United States)

    Badawi, M A; Negm, N A; Abou Kana, M T H; Hefni, H H; Abdel Moneem, M M

    2017-06-01

    Chitosan was reacted by tannic acid to obtain three modified chitosan biopolymer. Their chemical structures were characterized by FTIR and elemental analysis. The prepared biopolymers were used to adsorb Al(III) and Pb(II) metal ions from industrial wastewater. The factors affecting the adsorption process were biosorbent amount, initial concentration of metal ion and pH of the medium. The adsorption efficiency increased considerably with the increase of the biosorbent amount and pH of the medium. The adsorption process of biosorbent on different metal ions was fitted by Freundlich adsorption model. The adsorption kinetics was followed Pseudo-second-order kinetic model. The adsorption process occurred according to diffusion mechanism which was confirmed by the interparticle diffusion model. The modified biopolymers were efficient biosorbents for removal of Pb(II) and Al(III) metal ions from the medium. Copyright © 2017 Elsevier B.V. All rights reserved.

  18. p-Nitrophenol degradation by electro-Fenton process: Pathway, kinetic model and optimization using central composite design.

    Science.gov (United States)

    Meijide, J; Rosales, E; Pazos, M; Sanromán, M A

    2017-10-01

    The chemical process scale-up, from lab studies to industrial production, is challenging and requires deep knowledge of the kinetic model and the reactions that take place in the system. This knowledge is also useful in order to be employed for the reactor design and the determination of the optimal operational conditions. In this study, a model substituted phenol such as p-nitrophenol was degraded by electro-Fenton process and the reaction products yielded along the treatment were recorded. The kinetic model was developed using Matlab software and was based on main reactions that occurred until total mineralization which allowed predicting the degradation pathway under this advanced oxidation process. The predicted concentration profiles of p-nitrophenol, their intermediates and by-products in electro-Fenton process were validated with experimental assays and the results were consistent. Finally, based on the developed kinetic model the degradation process was optimized using central composite design taking as key parameters the ferrous ion concentration and current density. Copyright © 2017 Elsevier Ltd. All rights reserved.

  19. On-the-Fly Kinetic Monte Carlo Simulation of Aqueous Phase Advanced Oxidation Processes.

    Science.gov (United States)

    Guo, Xin; Minakata, Daisuke; Crittenden, John

    2015-08-04

    We have developed an on-the-fly kinetic Monte Carlo (KMC) model to predict the degradation mechanisms and fates of intermediates and byproducts that are produced during aqueous-phase advanced oxidation processes (AOPs). The on-the-fly KMC model is composed of a reaction pathway generator, a reaction rate constant estimator, a mechanistic reduction module, and a KMC solver. The novelty of this work is that we develop the pathway as we march forward in time rather than developing the pathway before we use the KMC method to solve the equations. As a result, we have fewer reactions to consider, and we have greater computational efficiency. We have verified this on-the-fly KMC model for the degradation of polyacrylamide (PAM) using UV light and titanium dioxide (i.e., UV/TiO2). Using the on-the-fly KMC model, we were able to predict the time-dependent profiles of the average molecular weight for PAM. The model provided detailed and quantitative insights into the time evolution of the molecular weight distribution and reaction mechanism. We also verified our on-the-fly KMC model for the destruction of (1) acetone, (2) trichloroethylene (TCE), and (3) polyethylene glycol (PEG) for the ultraviolet light and hydrogen peroxide AOP. We demonstrated that the on-the-fly KMC model can achieve the same accuracy as the computer-based first-principles KMC (CF-KMC) model, which has already been validated in our earlier work. The on-the-fly KMC is particularly suitable for molecules with large molecular weights (e.g., polymers) because the degradation mechanisms for large molecules can result in hundreds of thousands to even millions of reactions. The ordinary differential equations (ODEs) that describe the degradation pathways cannot be solved using traditional numerical methods, but the KMC can solve these equations.

  20. Kinetic modelling of anaerobic hydrolysis of solid wastes, including disintegration processes

    Energy Technology Data Exchange (ETDEWEB)

    García-Gen, Santiago [Department of Chemical Engineering, Institute of Technology, University of Santiago de Compostela, 15782 Santiago de Compostela (Spain); Sousbie, Philippe; Rangaraj, Ganesh [INRA, UR50, Laboratoire de Biotechnologie de l’Environnement, Avenue des Etangs, Narbonne F-11100 (France); Lema, Juan M. [Department of Chemical Engineering, Institute of Technology, University of Santiago de Compostela, 15782 Santiago de Compostela (Spain); Rodríguez, Jorge, E-mail: jrodriguez@masdar.ac.ae [Department of Chemical Engineering, Institute of Technology, University of Santiago de Compostela, 15782 Santiago de Compostela (Spain); Institute Centre for Water and Environment (iWater), Masdar Institute of Science and Technology, PO Box 54224 Abu Dhabi (United Arab Emirates); Steyer, Jean-Philippe; Torrijos, Michel [INRA, UR50, Laboratoire de Biotechnologie de l’Environnement, Avenue des Etangs, Narbonne F-11100 (France)

    2015-01-15

    Highlights: • Fractionation of solid wastes into readily and slowly biodegradable fractions. • Kinetic coefficients estimation from mono-digestion batch assays. • Validation of kinetic coefficients with a co-digestion continuous experiment. • Simulation of batch and continuous experiments with an ADM1-based model. - Abstract: A methodology to estimate disintegration and hydrolysis kinetic parameters of solid wastes and validate an ADM1-based anaerobic co-digestion model is presented. Kinetic parameters of the model were calibrated from batch reactor experiments treating individually fruit and vegetable wastes (among other residues) following a new protocol for batch tests. In addition, decoupled disintegration kinetics for readily and slowly biodegradable fractions of solid wastes was considered. Calibrated parameters from batch assays of individual substrates were used to validate the model for a semi-continuous co-digestion operation treating simultaneously 5 fruit and vegetable wastes. The semi-continuous experiment was carried out in a lab-scale CSTR reactor for 15 weeks at organic loading rate ranging between 2.0 and 4.7 g VS/L d. The model (built in Matlab/Simulink) fit to a large extent the experimental results in both batch and semi-continuous mode and served as a powerful tool to simulate the digestion or co-digestion of solid wastes.

  1. Determination and modeling of the influence of the fluid-dynamics in hydro-treating bench scale plants

    Energy Technology Data Exchange (ETDEWEB)

    Burkhardt, T.

    1999-09-16

    At an industrial scale, the hydro-treating of oil fractions is carried out in multiphase fixed bed reactors. The oil and hydrogen cross the catalyst bed, usually in co-current downflow. Since the product specifications are steadily becoming more severe, the testing of new catalysts and of modified operating conditions in pilot plants becomes increasingly important. Although these pilot plants are frequently by a factor of 100 000 smaller than the industrial units, they still have to allow the up-scaling to industrial units. In the literature relatively low conversion degrees in pilot plants are frequently reported, especially in downflow. The significantly lower fluid velocities in pilot plants seem to be responsible for such differences, as the influence of fluid-dynamic non-idealities and of the extra-particle mass transfer phenomena increases with a decrease of the fluid velocities. In the present work, the influence of important fluid-dynamic non-idealities on the hydro-treating of gas oil fractions in pilot plants was examined. This was done on the one hand in experiments with different pilot plants and on the other hand by simulations with an especially developed multiphase model. The phenomena were considered as well in an isolated manner. In order to examine any interactions with the chemical reactions, they were also studied in a reactive system. This methodology was applied to the phenomena, 'axial dispersion'and 'gas-liquid mass transfer'. (author)

  2. Conversion of Oleum papaveris seminis oil into methyl esters via esterification process: Optimization and kinetic study

    Directory of Open Access Journals (Sweden)

    Syam, A. M.

    2016-03-01

    Full Text Available This paper presents an acid pre-treatment process and a kinetic study for the esterification reaction of Oleum papaveris seminis oil with methanol in the presence of amberlite 120 as a solid catalyst to convert the oil into methyl esters. Response surface methodology (RSM was applied to optimize the reaction parameters, i.e. reaction time, percentage of the catalyst and volume ratio of methanol to oil. The results revealed that 0.87% w/w of catalyst concentration and 44.70% v/v of methanol to oil ratio provided final free fatty acid (FFA contents of 0.60% w/w at 102.40 min of reaction time. It proved that the contribution of Amberlite 120 in the esterification of FFA was highly significant. The kinetics of the esterification in Oleum papaveris seminis oil with methanol in the presence of the amberlite 120 catalyst were also investigated to establish the reaction rate constant (k, reaction order, and activation energy. The study was performed under the optimized parameters at three reaction temperatures (50, 55, and 60 ºC. The value of k was in the range of 0.013 to 0.027 min-1. The first-order kinetics’ model was suitable for this irreversible FFA esterification with the activation energy of about 60.9 KJ·mol-1.En este artículo se presenta un proceso de pre-tratamiento con ácido, y un estudio cinético de la reacción de esterificación. Se utiliza Oleum papaveris seminis con metanol en presencia de Amberlite 120 como catalizador sólido para la formación de los ésteres metílicos. Se aplicó una metodología de superficie de respuesta (RSM para optimizar los parámetros de la reacción; es decir, tiempo de reacción, porcentaje de la relación de catalizador y volumen de metanol - aceite. Los resultados mostraron que el 0,87% w/w de la concentración de catalizador y 44,70% v/v de metanol en relación al aceite dan lugar a un contenido final de ácidos grasos libres (FFA de 0,60% w/w en 102,40 min de tiempo de reacción. Se demostr

  3. Kinetics and mechanisms of elementary chemical processes of importance in combustion

    International Nuclear Information System (INIS)

    Munk, J.; Pagsberg, P.; Ratajczak, E.; Sztuba, B.; Sillesen, A.

    1988-01-01

    The technique of pulse radiolysis combined with transient ultraviolet absorption spectrophotometry has been employed in spectrokinetic studies of shortlived free radical intermediates of importance in combustion. Various source reactions for vinyl, propargyl and carboxyl radicals have been investigated and the UV-spectra of these radicals have been recorded. The spectral features have been utilized in kinetic studies of the self-reactions of the radicals and the reactions with oxygen. Kinetic results on the reaction NO + NH 2 are also reported. 10 refs. (author)

  4. Spectrophotometric Analysis of the Kinetic of Pd(II Chloride Complex Ions Sorption Process from Diluted Aqua Solutions Using Commercially Available Activated Carbon

    Directory of Open Access Journals (Sweden)

    Wojnicki M.

    2017-12-01

    Full Text Available In this paper, results of adsorption kinetic studies of Pd(II chloride complex ions on activated carbon Organosrob 10 CO are presented. Spectorphotometrical method was applied to investigate the process. Kinetic model was proposed, and fundamental thermodynamic parameters were determined. Proposed kinetic model describes well observed phenomenon in the studied range of concentration of Pd(II chloride complex ions as well, as concentration of activated carbon.

  5. Kinetic Study of Crystallization Process in Fe32Ni36Cr14P12B6 Metallic Glass

    International Nuclear Information System (INIS)

    Lad, Kirit; Pratap, Arun; Rao, T. L. Shanker

    2010-01-01

    Kinetics of crystallization process in a Fe-based metallic glass 2826A (Fe 32 Ni 36 Cr 14 P 12 B 6 ) has been studied with the help of differential scanning calorimetry(DSC). It is found that the 2826A metallic glass exhibits two overlapping crystallization peaks. The activation energy for crystallization (E) and the Avrami exponent (n) for the two crystallization peaks have been obtained using the Kolmogorov-Jhonson-Mehl-Avrami (KJMA) equation. The so-obtained values of E and n have been utilized to derive normalized heat flow curves. It has been observed that the theoretical heat flow curves obtained using KJMA equation show large deviations from the experimental curves for the first peak whereas the curves are in very close agreement for the second peak. This suggests that kinetics of crystallization process during the first peak cannot be described correctly in KJMA formalism.

  6. Kinetic Study of Crystallization Process in Fe32Ni36Cr14P12B6 Metallic Glass

    Science.gov (United States)

    Lad, Kirit; Rao, T. L. Shanker; Pratap, Arun

    2010-06-01

    Kinetics of crystallization process in a Fe-based metallic glass 2826A (Fe32Ni36Cr14P12B6) has been studied with the help of differential scanning calorimetry(DSC). It is found that the 2826A metallic glass exhibits two overlapping crystallization peaks. The activation energy for crystallization (E) and the Avrami exponent (n) for the two crystallization peaks have been obtained using the Kolmogorov-Jhonson-Mehl-Avrami (KJMA) equation. The so-obtained values of E and n have been utilized to derive normalized heat flow curves. It has been observed that the theoretical heat flow curves obtained using KJMA equation show large deviations from the experimental curves for the first peak whereas the curves are in very close agreement for the second peak. This suggests that kinetics of crystallization process during the first peak cannot be described correctly in KJMA formalism.

  7. Process and kinetics of the fundamental radiation-electrochemical reactions in the primary coolant loop of nuclear reactors

    International Nuclear Information System (INIS)

    Kozomara-Maic, S.

    1987-06-01

    In spite of the rather broad title of this report, its major part is devoted to the corrosion problems at the RA reactor, i.e. causes and consequences of the reactor shutdown in 1979 and 1982. Some problems of reactor chemistry are pointed out because they are significant for future reactor operation. The final conclusion of this report is that corrosion processes in the primary coolant circuit of the nuclear reactor are specific and that radiation effects cannot be excluded when processes and reaction kinetics are investigated. Knowledge about the kinetics of all the chemical reactions occurring in the primary coolant loop are of crucial significance for safe and economical reactor operation [sr

  8. THE MATHEMATICAL MODEL DEVELOPMENT OF THE ETHYLBENZENE DEHYDROGENATION PROCESS KINETICS IN A TWO-STAGE ADIABATIC CONTINUOUS REACTOR

    Directory of Open Access Journals (Sweden)

    V. K. Bityukov

    2015-01-01

    Full Text Available The article is devoted to the mathematical modeling of the kinetics of ethyl benzene dehydrogenation in a two-stage adiabatic reactor with a catalytic bed functioning on continuous technology. The analysis of chemical reactions taking place parallel to the main reaction of styrene formation has been carried out on the basis of which a number of assumptions were made proceeding from which a kinetic scheme describing the mechanism of the chemical reactions during the dehydrogenation process was developed. A mathematical model of the dehydrogenation process, describing the dynamics of chemical reactions taking place in each of the two stages of the reactor block at a constant temperature is developed. The estimation of the rate constants of direct and reverse reactions of each component, formation and exhaustion of the reacted mixture was made. The dynamics of the starting material concentration variations (ethyl benzene batch was obtained as well as styrene formation dynamics and all byproducts of dehydrogenation (benzene, toluene, ethylene, carbon, hydrogen, ect.. The calculated the variations of the component composition of the reaction mixture during its passage through the first and second stages of the reactor showed that the proposed mathematical description adequately reproduces the kinetics of the process under investigation. This demonstrates the advantage of the developed model, as well as loyalty to the values found for the rate constants of reactions, which enable the use of models for calculating the kinetics of ethyl benzene dehydrogenation under nonisothermal mode in order to determine the optimal temperature trajectory of the reactor operation. In the future, it will reduce energy and resource consumption, increase the volume of produced styrene and improve the economic indexes of the process.

  9. Influence of film structure on the dewetting kinetics of thin polymer films in the solvent annealing process.

    Science.gov (United States)

    Zhang, Huanhuan; Xu, Lin; Lai, Yuqing; Shi, Tongfei

    2016-06-28

    On a non-wetting solid substrate, the solvent annealing process of a thin polymer film includes the swelling process and the dewetting process. Owing to difficulties in the in situ analysis of the two processes simultaneously, a quantitative study on the solvent annealing process of thin polymer films on the non-wetting solid substrate is extremely rare. In this paper, we design an experimental method by combining spectroscopic ellipsometry with optical microscopy to achieve the simultaneous in situ study. Using this method, we investigate the influence of the structure of swollen film on its dewetting kinetics during the solvent annealing process. The results show that for a thin PS film with low Mw (Mw = 4.1 kg mol(-1)), acetone molecules can form an ultrathin enriched layer between the PS film and the solid substrate during the swelling process. The presence of the acetone enriched layer accounts for the exponential kinetic behavior in the case of a thin PS film with low Mw. However, the acetone enriched layer is not observed in the case of a thin PS film with high Mw (Mw = 400 kg mol(-1)) and the slippage effect of polymer chains is valid during the dewetting process.

  10. Production of bio-hydrogenated diesel by catalytic hydrotreating of palm oil over NiMoS2/γ-Al2O3 catalyst.

    Science.gov (United States)

    Srifa, Atthapon; Faungnawakij, Kajornsak; Itthibenchapong, Vorranutch; Viriya-Empikul, Nawin; Charinpanitkul, Tawatchai; Assabumrungrat, Suttichai

    2014-04-01

    Catalytic hydrotreating of palm oil (refined palm olein type) to produce bio-hydrogenated diesel (BHD) was carried out in a continuous-flow fixed-bed reactor over NiMoS2/γ-Al2O3 catalyst. Effects of dominant hydrotreating parameters: temperature: 270-420°C; H2 pressure: 15-80 bar; LHSV: 0.25-5.0 h(-1); and H2/oil ratio: 250-2000 N(cm(3)/cm(3)) on the conversion, product yield, and a contribution of hydrodeoxygenation (HDO) and decarbonylation/decarboxylation (DCO/DCO2) were investigated to find the optimal hydrotreating conditions. All calculations including product yield and the contribution of HDO and DCO/DCO2 were extremely estimated based on mole balance corresponding to the fatty acid composition in feed to fully understand deoxygenation behaviors at different conditions. These analyses demonstrated that HDO, DCO, and DCO2 reactions competitively occurred at each condition, and had different optimal and limiting conditions. The differences in the hydrotreating reactions, liquid product compositions, and gas product composition were also discussed. Copyright © 2014 Elsevier Ltd. All rights reserved.

  11. Evaluation of Degradation Kinetic of Tomato Paste Color in Heat Processing and Modeling of These Changes by Response Surface Methodology

    Directory of Open Access Journals (Sweden)

    M. Ganjeh

    2015-12-01

    Full Text Available Color is an important qualitative factor in tomato products such as tomato paste which is affected by heat processing. The main goal of this study was to evaluate the degradation kinetics of tomato paste color during heat processing by Arrhenius equation and modeling of these changes by response surface methodology (RSM. Considering this purpose, tomato paste was processed at three temperatures of 60, 70 and 80 °C for 25-100 minutes and by three main color indices including L, a and b, a/b ratio, total color difference (TCD, Saturation index (SI and hue angle (HU was analyzed. Degradation kinetics of these parameters was evaluated by Arrhenius equation and their changing trends were modeled by RSM. All parameters except TCA (zero order followed a first order reaction. The b index by highest and TCA and a/b by least activation energies had the maximum and minimum sensitivity to the temperature changes, respectively. Also, TCD and b had the maximum and minimum changing rates, respectively. All responses were influenced by independent parameters (the influence of temperature was more than time and RSM was capable of modeling and predicting these responses. In general, Arrhenius equation was appropriate to evaluate degradation kinetics of tomato paste color changes and RSM was able to estimate independent and interaction effects of time and temperature so that quadratic models were capable to predict these changes by a high accuracy (R2 > 0.95.

  12. Observations on the properties of second and general-order kinetics equations describing the thermoluminescence processes

    International Nuclear Information System (INIS)

    Kitis, G.; Furetta, C.; Azorin, J.

    2003-01-01

    Synthetic thermoluminescent (Tl) glow peaks, following a second and general kinetics order have been generated by computer. The general properties of the so generated peaks have been investigated over several order of magnitude of simulated doses. Some non usual results which, at the best knowledge of the authors, are not reported in the literature, are obtained and discussed. (Author)

  13. Kinetic analyses and mathematical modeling of primary photochemical and photoelectrochemical processes in plant photosystems

    NARCIS (Netherlands)

    Vredenberg, W.J.

    2011-01-01

    In this paper the model and simulation of primary photochemical and photo-electrochemical reactions in dark-adapted intact plant leaves is presented. A descriptive algorithm has been derived from analyses of variable chlorophyll a fluorescence and P700 oxidation kinetics upon excitation with

  14. Determination of Kinetic Parameters of Coal Pyrolysis to Simulate the Process of Underground Coal Gasification (UCG

    Directory of Open Access Journals (Sweden)

    Beata Urych

    2014-01-01

    Originality/value: The devolatilization of a homogenous lump of coal is a complex issue. Currently, the CFD technique (Computational Fluid Dynamics is commonly used for the multi-dimensional and multiphase phenomena modelling. The mathematical models, describing the kinetics of the decomposition of coal, proposed in the article can, therefore, be an integral part of models based on numerical fluid mechanics.

  15. Dynamic Model of Basic Oxygen Steelmaking Process Based on Multizone Reaction Kinetics: Modeling of Decarburization

    Science.gov (United States)

    Rout, Bapin Kumar; Brooks, Geoffrey; Akbar Rhamdhani, M.; Li, Zushu; Schrama, Frank N. H.; Overbosch, Aart

    2018-03-01

    In a previous study by the authors (Rout et al. in Metall Mater Trans B 49:537-557, 2018), a dynamic model for the BOF, employing the concept of multizone kinetics was developed. In the current study, the kinetics of decarburization reaction is investigated. The jet impact and slag-metal emulsion zones were identified to be primary zones for carbon oxidation. The dynamic parameters in the rate equation of decarburization such as residence time of metal drops in the emulsion, interfacial area evolution, initial size, and the effects of surface-active oxides have been included in the kinetic rate equation of the metal droplet. A modified mass-transfer coefficient based on the ideal Langmuir adsorption equilibrium has been proposed to take into account the surface blockage effects of SiO2 and P2O5 in slag on the decarburization kinetics of a metal droplet in the emulsion. Further, a size distribution function has been included in the rate equation to evaluate the effect of droplet size on reaction kinetics. The mathematical simulation indicates that decarburization of the droplet in the emulsion is a strong function of the initial size and residence time. A modified droplet generation rate proposed previously by the authors has been used to estimate the total decarburization rate by slag-metal emulsion. The model's prediction shows that about 76 pct of total carbon is removed by reactions in the emulsion, and the remaining is removed by reactions at the jet impact zone. The predicted bath carbon by the model has been found to be in good agreement with the industrially measured data.

  16. Dynamic Model of Basic Oxygen Steelmaking Process Based on Multizone Reaction Kinetics: Modeling of Decarburization

    Science.gov (United States)

    Rout, Bapin Kumar; Brooks, Geoffrey; Akbar Rhamdhani, M.; Li, Zushu; Schrama, Frank N. H.; Overbosch, Aart

    2018-06-01

    In a previous study by the authors (Rout et al. in Metall Mater Trans B 49:537-557, 2018), a dynamic model for the BOF, employing the concept of multizone kinetics was developed. In the current study, the kinetics of decarburization reaction is investigated. The jet impact and slag-metal emulsion zones were identified to be primary zones for carbon oxidation. The dynamic parameters in the rate equation of decarburization such as residence time of metal drops in the emulsion, interfacial area evolution, initial size, and the effects of surface-active oxides have been included in the kinetic rate equation of the metal droplet. A modified mass-transfer coefficient based on the ideal Langmuir adsorption equilibrium has been proposed to take into account the surface blockage effects of SiO2 and P2O5 in slag on the decarburization kinetics of a metal droplet in the emulsion. Further, a size distribution function has been included in the rate equation to evaluate the effect of droplet size on reaction kinetics. The mathematical simulation indicates that decarburization of the droplet in the emulsion is a strong function of the initial size and residence time. A modified droplet generation rate proposed previously by the authors has been used to estimate the total decarburization rate by slag-metal emulsion. The model's prediction shows that about 76 pct of total carbon is removed by reactions in the emulsion, and the remaining is removed by reactions at the jet impact zone. The predicted bath carbon by the model has been found to be in good agreement with the industrially measured data.

  17. Numerical studies of spray combustion processes of palm oil biodiesel and diesel fuels using reduced chemical kinetic mechanisms

    KAUST Repository

    Kuti, Olawole

    2014-04-01

    Spray combustion processes of palm oil biodiesel (PO) and conventional diesel fuels were simulated using the CONVERGE CFD code. Thermochemical and reaction kinetic data (115 species and 460 reactions) by Luo et al. (2012) and Lu et al. (2009) (68 species and 283 reactions) were implemented in the CONVERGE CFD to simulate the spray and combustion processes of the two fuels. Tetradecane (C14H30) and n- heptane (C7H 16) were used as surrogates for diesel. For the palm biodiesel, the mixture of methyl decanoate (C11H20O2), methyl-9-decenoate (C11H19O2) and n-heptane was used as surrogate. The palm biodiesel surrogates were combined in proportions based on the previous GC-MS results for the five major biodiesel components namely methyl palmitate, methyl stearate, methyl oleate, methyl linoleate and methyl linolenate. The Favre-Averaged Navier Stokes based simulation using the renormalization group (RNG) k-ε turbulent model was implemented in the numerical calculations of the spray formation processes while the SAGE chemical kinetic solver is used for the detailed kinetic modeling. The SAGE chemical kinetic solver is directly coupled with the gas phase calculations by renormalization group (RNG) k-ε turbulent model using a well-stirred reactor model. Validations of the spray liquid length, ignition delay and flame lift-off length data were performed against previous experimental results. The simulated liquid length, ignition delay and flame lift-off length were validated at an ambient density of 15kg/m3, and injection pressure conditions of 100, 200 and 300 MPa were utilized. The predicted liquid length, ignition delay and flame lift-off length agree with the trends obtained in the experimental data at all injection conditions. Copyright © 2014 SAE International.

  18. water alteration processes and kinetics of basaltic glasses, natural analogue of nuclear glasses

    International Nuclear Information System (INIS)

    Techer, I.; Advocat, Th.; Vernaz, E.; Lancelot, J.R.; Liotard, J.M.

    1997-01-01

    Dissolution experiments of a basaltic glass were carried out at 90 deg C for different reaction progresses. The initial dissolution rate was compared with values obtained for rhyolitic glass and the R7T7 nuclear glass. The activation energy was also determined by computing literature data. The results provide similar reactional mechanism for basaltic and nuclear glasses. Dissolution rates measured under saturation conditions were compared to theoretical dissolution rates. These ones were calculated using two kinetic models: the first rate equation is the Grambow's law which only takes into account ortho-silica acid activity; the second rate equation was proposed by Daux et al., where silica and aluminum are combined to formulate the affinity. The comparison between experimental and theoretical results point out that these two models are not appropriate to describe the alteration kinetic of basaltic glasses. (authors)

  19. The silver catalyst process for converting methanol to formaldehyde - kinetic investigations

    Energy Technology Data Exchange (ETDEWEB)

    Panzer, E.; Emig, G. [Erlangen-Nuernberg Univ., Erlangen (Germany). Lehrstuhl fuer Technische Chemie 1

    1998-12-31

    In pre-experiments a tubular reactor was checked whether it is suitable for kinetic measurement on the system of the silver-catalysed partial oxidation of methanol to formaldehyde. Detrimental effects of heat-transfer and mass-transfer on the experimental results were ruled out. Investigations on the characteristics of the reaction showed that it is possible to manipulate the composition of the product mixture by changing the inlet concentration of the reactants. A modified power-law model was established to describe the reaction kinetics. It considers the preadsorption step of oxygen on the catalysts surface and fits the experimental data quite well. During the rapid oxidation the catalysts surface undergoes a drastic change. It gets coarse and has an adsorption capacity of 11 m{sup 2}/g after being exposed to the reaction mixture. (orig.)

  20. Kinetics of photochromic processes in substituted dihydropyridines in the solid state and in solution

    Czech Academy of Sciences Publication Activity Database

    Sworakowski, J.; Nešpůrek, Stanislav; Lipinski, J.; Lewanowicz, A.; Sliwinska, E.

    2001-01-01

    Roč. 356, - (2001), s. 163-173 ISSN 1058-725X. [International Conference on the Chemistry of the Organic Solid State /14./. Cambridge, 25.07.1999-30.07.1999] R&D Projects: GA AV ČR IAA1050901; GA AV ČR KSK4050111 Institutional research plan: CEZ:AV0Z4050913 Keywords : dihydropyridine * photochromism * reaction kinetics Subject RIV: CD - Macromolecular Chemistry Impact factor: 0.457, year: 2001

  1. Lithium and rubidium extraction from zinnwaldite by alkali digestion process: Sintering mechanism and leaching kinetics

    Czech Academy of Sciences Publication Activity Database

    Vu, H.; Bernardi, J.; Jandová, J.; Vaculíková, Lenka; Goliáš, V.

    2013-01-01

    Roč. 123, č. 1 (2013), s. 9-17 ISSN 0301-7516 R&D Projects: GA MŠk ED2.1.00/03.0082 Institutional support: RVO:68145535 Keywords : zinnwaldite * lithium * rubidium * sintering mechanism * leaching kinetics Subject RIV: CB - Analytical Chemistry, Separation Impact factor: 1.461, year: 2013 http://www.sciencedirect.com/science/article/pii/S0301751613001087

  2. Kinetic evidence of an apparent negative activation enthalpy in an organocatalytic process

    KAUST Repository

    Han, Xiao

    2013-08-30

    A combined kinetic and computational study on our tryptophan-based bifunctional thiourea catalyzed asymmetric Mannich reactions reveals an apparent negative activation enthalpy. The formation of the pre-transition state complex has been unambiguously confirmed and these observations provide an experimental support for the formation of multiple hydrogen bonding network between the substrates and the catalyst. Such interactions allow the creation of a binding cavity, a key factor to install high enantioselectivity.

  3. Kinetic evidence of an apparent negative activation enthalpy in an organocatalytic process

    KAUST Repository

    Han, Xiao; Lee, Richmond; Chen, Tao; Luo, Jie; Lu, Yixin; Huang, Kuo-Wei

    2013-01-01

    A combined kinetic and computational study on our tryptophan-based bifunctional thiourea catalyzed asymmetric Mannich reactions reveals an apparent negative activation enthalpy. The formation of the pre-transition state complex has been unambiguously confirmed and these observations provide an experimental support for the formation of multiple hydrogen bonding network between the substrates and the catalyst. Such interactions allow the creation of a binding cavity, a key factor to install high enantioselectivity.

  4. Large scale synthesis of α-Si3N4 nanowires through a kinetically favored chemical vapour deposition process

    Science.gov (United States)

    Liu, Haitao; Huang, Zhaohui; Zhang, Xiaoguang; Fang, Minghao; Liu, Yan-gai; Wu, Xiaowen; Min, Xin

    2018-01-01

    Understanding the kinetic barrier and driving force for crystal nucleation and growth is decisive for the synthesis of nanowires with controllable yield and morphology. In this research, we developed an effective reaction system to synthesize very large scale α-Si3N4 nanowires (hundreds of milligrams) and carried out a comparative study to characterize the kinetic influence of gas precursor supersaturation and liquid metal catalyst. The phase composition, morphology, microstructure and photoluminescence properties of the as-synthesized products were characterized by X-ray diffraction, fourier-transform infrared spectroscopy, field emission scanning electron microscopy, transmission electron microscopy and room temperature photoluminescence measurement. The yield of the products not only relates to the reaction temperature (thermodynamic condition) but also to the distribution of gas precursors (kinetic condition). As revealed in this research, by controlling the gas diffusion process, the yield of the nanowire products could be greatly improved. The experimental results indicate that the supersaturation is the dominant factor in the as-designed system rather than the catalyst. With excellent non-flammability and high thermal stability, the large scale α-Si3N4 products would have potential applications to the improvement of strength of high temperature ceramic composites. The photoluminescence spectrum of the α-Si3N4 shows a blue shift which could be valued for future applications in blue-green emitting devices. There is no doubt that the large scale products are the base of these applications.

  5. First experimental results on the kinetic processes in a surface-wave-sustained argon discharge at atmospheric pressure

    International Nuclear Information System (INIS)

    Calzada, M.D.; Gamero, A.; Sola, A.

    1995-01-01

    This communication presents an advance of the results of an experimental study of the kinetic processes in a surface-wave-sustained argon discharge at atmospheric pressure. We utilize the study developed by Fujimoto on the population and depopulation processes of the excited levels of atoms and ions. This theory has been applied by S. Daviaud and A. Hirabayashi to explain the kinetic processes in helium plasma at low pressure. Fujimoto has studied the ionization and recombination mechanisms of the plasma under various conditions and its relation to the population density distributions. This study establishes, for an hydrogenic ion with a core charge z, different zones in the atomic system (level map). Each zone is characterized by the dominant mechanisms of the population and depopulation of their excited levels, A level is characterized for the effective principal quantum number p, where p = z (E H /|E p |) 1/2 , E H is the hydrogen ionization energy and |E p | is the energy required to ionize the atom from the level considered. The population of each level p can be expressed in terms of the parameter b(p) defined as n(p)/n SB (p), n(p) and n SB (p) being the actual population and the Saha-Boltzmann equilibrium population of the level, respectively. Figure I shows the population and depopulation processes of a level p, which are both collisional and radiative that are characterized by their respective coefficients

  6. Kinetic model of continuous ethanol fermentation in closed-circulating process with pervaporation membrane bioreactor by Saccharomyces cerevisiae.

    Science.gov (United States)

    Fan, Senqing; Chen, Shiping; Tang, Xiaoyu; Xiao, Zeyi; Deng, Qing; Yao, Peina; Sun, Zhaopeng; Zhang, Yan; Chen, Chunyan

    2015-02-01

    Unstructured kinetic models were proposed to describe the principal kinetics involved in ethanol fermentation in a continuous and closed-circulating fermentation (CCCF) process with a pervaporation membrane bioreactor. After ethanol was removed in situ from the broth by the membrane pervaporation, the secondary metabolites accumulated in the broth became the inhibitors to cell growth. The cell death rate related to the deterioration of the culture environment was described as a function of the cell concentration and fermentation time. In CCCF process, 609.8 g L(-1) and 750.1 g L(-1) of ethanol production were obtained in the first run and second run, respectively. The modified Gompertz model, correlating the ethanol production with the fermentation period, could be used to describe the ethanol production during CCCF process. The fitting results by the models showed good agreement with the experimental data. These models could be employed for the CCCF process technology development for ethanol fermentation. Copyright © 2014 Elsevier Ltd. All rights reserved.

  7. Degradation kinetics of reactive dye by UV/H2O2/US process under continuous mode operation.

    Science.gov (United States)

    Fung, P C; Poon, C S; Chu, C W; Tsui, S M

    2001-01-01

    Degradation of a dye, C. I . Reactive Red 120, in dyeing waatewater by the process o UV/H2O2/US was studied with a bench-scale reactor under the continuous mode of operation. The effects of dyeing wastewater flow rate and the feeding rate of an oxidant, H2O2, on the color removal efficiency of the process were investigated. The significance of ultrasonic (US) combined with UV irradiation was also investigated and the performances of the process on color removal were evaluated. The results showed that the decoloration process followed a pseudo first-order kinetic model and the UV light is the most significant factor on dye removal. Besides, at higher flow rates, incomplete color removal was observed due to relatively insufficient irradiation time (low degradation rate). In order to achieve a higher degradation rate, the feeding rate of H2O2 should be increased.

  8. Collection and processing of information in biological kinetics studies with radioactive tracers

    International Nuclear Information System (INIS)

    Remy, J.; Lafuma, J.

    1968-01-01

    The authors present an automatic method for the collection and treatment of information in biological kinetics experiments using radioactive tracers. The recording are made without any time constant on magnetic tape. The information recorded is sampled by a 400 channel multi-scale analyzer and transferred to punched cards. The digital analysis is done by an I.B.M. computer. The method is illustrated by an example: the hepatic fixation of colloidal gold in the pig. Its advantages and requirements are discussed. In the appendix are given the FORTRAN texts for two programmes used in treating the example presented. (authors) [fr

  9. Isotherm, kinetic and thermodynamics study of humic acid removal process from aquatic environment by chitosan nano particle

    Directory of Open Access Journals (Sweden)

    Maryam Ghafoori

    2016-09-01

    Full Text Available Background and Aim: Humic substances include natural organic polyelectrolyte materials that formed most of the dissolved organic carbon in aquatic environments. Reaction between humic substances and chlorine leading to formation of disinfection byproducts (DBPs those are toxic, carcinogenic and mutagenic. The aim of this study was investigation of isotherms, kinetics and thermodynamics of humic acid removal process by nano chitosan from aquatic environment. Materials and Methods: This practical research was an experimental study that performed in a batch system. The effect of various parameters such as pH, humic acid concentration, contact time, adsorbent dosage, isotherms, thermodynamics and Kinetics of humic acid adsorption process were investigated. Humic acid concentration measured using spectrophotometer at wave length of 254 nm. Results: The results of this research showed that maximum adsorption capacity of nanochitosan that fall out in concentration of 50 mg/l and contact time of 90 minutes was 52.34 mg/g. Also, the maximum adsorption was observed in pH = 4 and adsorbent dosage 0.02 g. Laboratory data show that adsorption of humic acid by nanochitosan follow the Langmuir isotherm model. According to result of thermodynamic study, entropy changes (ΔS was equal to 2.24 J/mol°k, enthalpy changes (ΔH was equal to 870 kJ/mol and Gibbs free energy (ΔG was negative that represent the adsorption process is spontaneous and endothermic. The kinetics of adsorption has a good compliant with pseudo second order model. Conclusion: Regarding to results of this study, nano chitosan can be suggested as a good adsorbent for the removal of humic acids from aqueous solutions.

  10. Laboratory testing results of kinetics and processing technology of the polymetallic sulphide concentrate Blagojev Kamen – Serbia

    Directory of Open Access Journals (Sweden)

    Milorad Ćirković

    2016-06-01

    Full Text Available This work presents the laboratory testing results of kinetics the oxidation process and sample processing of the sulphide polymetallic concentrate Blagojev Kamen. The aim of investigation is recovery of these types of raw material, present in large quantities in the peripheral parts of already used primary mineral deposits of copper, because of their high economic potential due to the content of a large number of metals and especially precious metals. Characterization of this raw material is based on the chemical analyses, XRD results, DTA analysis, etc. For these investigations, the sulphide concentrate with the following content was used in %: Cu – 2.3; Fe – 19.8; S – 27.19; Zn – 9.13; As – 0.167; Pb – 15.63; SiO2 – 17.93; CaO – 0.97; Al2O3 – 1.43; Ag – 480 g/t; Au – 659 g/t. Kinetic investigations of oxidation processes were carried out under the isothermal conditions within the temperature range of 400 to 625 oC. The Sharp's model was used for determination the kinetics parameters, and determined values of activation energy are 67 kJ/mole for the first period, and 47 kJ/mole for the second period. Pyrometallurgical treatment of this type of polymetallic concentrate, in the laboratory conditions, was carried out using the oxidative roasting and, then the reduction smelting was done in the Taman's furnace. Gold from 90.5 to 97.95% and silver from 77.28 to 93.37% are moved into the raw lead (smelting product. Gold from 1.1 to 3.92% and silver from 4.35 to 8.42% are moved into the polymetallic copper matte. Gold from 0.58 to 1.6% and silver from 2.45 to 6.82% are moved into the slag.

  11. The complex reaction kinetics of neptunium including redox and extraction process in 30% TBP-nitric acid system

    International Nuclear Information System (INIS)

    Hu Zhang; Zhan-yuan Liu; Xian-ming Zhou; Li Li

    2017-01-01

    In order to understand the complex and dynamic neptunium process chemistry in the TBP-HNO_3 system, the kinetics involved reversible redox reaction and extraction mass transfer was investigated. The results indicates that the mass transfer rate of Np(VI) is much faster than the redox reaction in aqueous solution. The concentrations of nitric acid and nitrous acid not only can change the Np(V) oxidation reaction and Np(VI) reduction reaction rate, but also can ultimately determine the distribution of neptunium extraction equilibrium. The variety of temperature can only influence the extraction equilibrium time, but cannot alter the equilibrium state of neptunium. (author)

  12. Degradation of the fungicide carbendazim in aqueous solutions with UV/TiO2 process: Optimization, kinetics and toxicity studies

    International Nuclear Information System (INIS)

    Saien, J.; Khezrianjoo, S.

    2008-01-01

    An attempt was made to investigate the potential of UV-photocatalytic process in the presence of TiO 2 particles for the degradation of carbendazim (C 9 H 9 N 3 O 2 ), a fungicide with a high worldwide consumption but considered as a 'priority hazard substance' by the Water Framework Directive of the European Commission (WFDEC). A circulating upflow photo-reactor was employed and the influence of catalyst concentration, pH and temperature were investigated. The results showed that degradation of this fungicide can be conducted in the both processes of only UV-irradiation and UV/TiO 2 ; however, the later provides much better results. Accordingly, a degradation of more than 90% of fungicide was achieved by applying the optimal operational conditions of 70 mg L -1 of catalyst, natural pH of 6.73 and ambient temperature of 25 deg. C after 75 min irradiation. Under these mild conditions, the initial rate of degradation can be described well by the Langmuir-Hinshelwood kinetic model. Toxicological assessments on the obtained samples were also performed by measurement of the mycelium growth inhibition of Fusarium oxysporum fungus on PDA medium. The results indicate that the kinetics of degradation and toxicity are in reasonably good agreement mainly after 45 min of irradiation; confirming the effectiveness of photocatalytic process

  13. Kinetics and

    Directory of Open Access Journals (Sweden)

    Mojtaba Ahmadi

    2016-11-01

    Full Text Available The aqueous degradation of Reactive Yellow 84 (RY84 by potassium peroxydisulfate (K2S2O8 has been studied in laboratory scale experiments. The effect of the initial concentrations of potassium peroxydisulfate and RY84, pH and temperature on RY84 degradation were also examined. Experimental data were analyzed using first and second-order kinetics. The degradation kinetics of RY84 of the potassium peroxydisulfate process followed the second-order reaction kinetics. These rate constants have an extreme values similar to of 9.493 mM−1min−1 at a peroxydisulfate dose of 4 mmol/L. Thermodynamic parameters such as activation (Ea and Gibbs free energy (ΔG° were also evaluated. The negative value of ΔGo and Ea shows the spontaneous reaction natural conditions and exothermic nature.

  14. Oxidation kinetics of innovative carbon materials with respect to severe air ingress accidents in HTRs and graphite disposal or processing

    International Nuclear Information System (INIS)

    Schloegel, Baerbel

    2010-01-01

    Currently future nuclear reactor concepts of the Fourth Generation (Gen IV) are under development. To some extend they apply with new, innovative materials developed just for this purpose. This thesis work aims at a concept of Generation IV Very High Temperature Reactors (VHTR) in the framework of the European project RAPHAEL (ReActor for Process heat, Hydrogen And ELectricity generation). The concept named ANTARES (AREVA New Technology based on advanced gas-cooled Reactors for Energy Supply) was developed by AEVA NP. It is a helium cooled, graphite moderated modular reactor for electricity and hydrogen production, by providing the necessary process heat due to its high working temperature. Particular attention is given here to oxidation kinetics of newly developed carbon materials (NBG-17) with still unknown but needed information in context of severe air ingress accident in VHTR's. Special interest is paid to the Boudouard reaction, the oxidation of carbon by CO 2 . In case of an air ingress accident, carbon dioxide is produced in the primary reaction of atmospheric oxygen with reflector graphite. From there CO 2 could flow into the reactor core causing further damage by conversion into CO. The purpose of this thesis is to ascertain if and to what degree this could happen. First of all oxidation kinetic data of the Boudouard reaction with NBG-17 is determined by experiments in a thermo gravimetric facility. The measurements are evaluated and converted into a common formula and a Langmuir-Hinshelwood similar oxidation kinetic equation, as input for the computer code REACT/THERMIX. This code is then applied to analyse severe air ingress accidents for several air flow rates. The results are discussed for two accident situations, in which a certain graphite burn off is achieved. All cases show much more damage to the graphite bottom reflector than to the reactor core. Thus the bottom reflector will lose its structural integrity much earlier than the core itself will

  15. DEVELOPMENT OF A KINETIC MODEL OF BOEHMITE DISSOLUTION IN CAUSTIC SOLUTIONS APPLIED TO OPTIMIZE HANFORD WASTE PROCESSING

    International Nuclear Information System (INIS)

    Disselkamp, R.S.

    2011-01-01

    Boehmite (e.g., aluminum oxyhydroxide) is a major non-radioactive component in Hanford and Savannah River nuclear tank waste sludge. Boehmite dissolution from sludge using caustic at elevated temperatures is being planned at Hanford to minimize the mass of material disposed of as high-level waste (HLW) during operation of the Waste Treatment Plant (WTP). To more thoroughly understand the chemistry of this dissolution process, we have developed an empirical kinetic model for aluminate production due to boehmite dissolution. Application of this model to Hanford tank wastes would allow predictability and optimization of the caustic leaching of aluminum solids, potentially yielding significant improvements to overall processing time, disposal cost, and schedule. This report presents an empirical kinetic model that can be used to estimate the aluminate production from the leaching of boehmite in Hanford waste as a function of the following parameters: (1) hydroxide concentration; (2) temperature; (3) specific surface area of boehmite; (4) initial soluble aluminate plus gibbsite present in waste; (5) concentration of boehmite in the waste; and (6) (pre-fit) Arrhenius kinetic parameters. The model was fit to laboratory, non-radioactive (e.g. 'simulant boehmite') leaching results, providing best-fit values of the Arrhenius A-factor, A, and apparent activation energy, E A , of A = 5.0 x 10 12 hour -1 and E A = 90 kJ/mole. These parameters were then used to predict boehmite leaching behavior observed in previously reported actual waste leaching studies. Acceptable aluminate versus leaching time profiles were predicted for waste leaching data from both Hanford and Savannah River site studies.

  16. A kinetic model for the first stage of pygas upgrading

    Directory of Open Access Journals (Sweden)

    J. L. de Medeiros

    2007-03-01

    Full Text Available Pyrolysis gasoline - PYGAS - is an intermediate boiling product of naphtha steam cracking with a high octane number and high aromatic/unsaturated contents. Due to stabilization concerns, PYGAS must be hydrotreated in two stages. The first stage uses a mild trickle-bed conversion for removing extremely reactive species (styrene, dienes and olefins prior to the more severe second stage where sulfured and remaining olefins are hydrogenated in gas phase. This work addresses the reaction network and two-phase kinetic model for the first stage of PYGAS upgrading. Nonlinear estimation was used for model tuning with kinetic data obtained in bench-scale trickle-bed hydrogenation with a commercial Pd/Al2O3 catalyst. On-line sampling experiments were designed to study the influence of variables - temperature and spatial velocity - on the conversion of styrene, dienes and olefins.

  17. Kinetics and Thermodynamics of DNA Processing by Wild Type DNA-Glycosylase Endo III and Its Catalytically Inactive Mutant Forms

    Directory of Open Access Journals (Sweden)

    Olga A. Kladova

    2018-03-01

    Full Text Available Endonuclease III (Endo III or Nth is one of the key enzymes responsible for initiating the base excision repair of oxidized or reduced pyrimidine bases in DNA. In this study, a thermodynamic analysis of structural rearrangements of the specific and nonspecific DNA-duplexes during their interaction with Endo III is performed based on stopped-flow kinetic data. 1,3-diaza-2-oxophenoxazine (tCO, a fluorescent analog of the natural nucleobase cytosine, is used to record multistep DNA binding and lesion recognition within a temperature range (5–37 °C. Standard Gibbs energy, enthalpy, and entropy of the specific steps are derived from kinetic data using Van’t Hoff plots. The data suggest that enthalpy-driven exothermic 5,6-dihydrouracil (DHU recognition and desolvation-accompanied entropy-driven adjustment of the enzyme–substrate complex into a catalytically active state play equally important parts in the overall process. The roles of catalytically significant amino acids Lys120 and Asp138 in the DNA lesion recognition and catalysis are identified. Lys120 participates not only in the catalytic steps but also in the processes of local duplex distortion, whereas substitution Asp138Ala leads to a complete loss of the ability of Endo III to distort a DNA double chain during enzyme–DNA complex formation.

  18. Connection between kinetic phenomena and atomic ordering processes and electronic structure of Ni3(FeMe)-type alloys

    International Nuclear Information System (INIS)

    Vasil'eva, R.P.; Arkhipov, Yu.N.; Narkulov, N.; Fadin, V.P.

    1978-01-01

    The results are presented of the measurements of the Hall and the Nernst-Ettingshausen effect and of thermal emf, electric resistivity and magnetization measurements in alloys Ni 3 (FeMe), where Me is Mo, Cr, W. The concentration of additions is not higher than 12.5%. The relationship of the kinetic phenomena with peculiarities of the electron structure and ordering processes is investigated. The obtained data show that the Hall and Nernst-Ettingshausen electromotive forces in the investigated alloys have positive values. The effects of the concentration variations of the investigated phenomena manifest themselves stronger in ordered state, this testifyies to a considerable increase of the part, the hole sections of the Fermi surface play. The investigation enables some conclusions to be made on the energy characteristics of these alloys as a function of the variation of the concentration composition of the alloys and the ordering processes

  19. Analysis of the laser oxidation kinetics process of In-In(2)O(3) MTMO photomasks by laser direct writing.

    Science.gov (United States)

    Xia, Feng; Zhang, Xinzheng; Wang, Meng; Liu, Qian; Xu, Jingjun

    2015-11-02

    One kind of novel grayscale photomask based on Metal-transparent-metallic-oxides (MTMOs) system fabricated by laser direct writing was demonstrated recently. Here, a multilayer oxidation model of In-In(2)O(3) film with a glass substrate was proposed to study the pulsed laser-induced oxidation mechanism. The distribution of the electromagnetic field in the film is calculated by the transfer matrix method. Temperature fields of the model are simulated based on the heat transfer equations with the Finite-Difference Time-Domain method. The oxidation kinetics process is studied based on the laser-induced Cabrera-Mott theory. The simulated oxidation processes are consistent with the experimental results, which mean that our laser-induced oxidation model can successfully interpret the fabrication mechanism of MTMO grayscale photomasks.

  20. Heart Rate and Oxygen Uptake Kinetics in Type 2 Diabetes Patients - A Pilot Study on the Influence of Cardiovascular Medication on Regulatory Processes.

    Science.gov (United States)

    Koschate, Jessica; Drescher, Uwe; Baum, Klaus; Brinkmann, Christian; Schiffer, Thorsten; Latsch, Joachim; Brixius, Klara; Hoffmann, Uwe

    2017-05-01

    The aim of this pilot study was to investigate whether there are differences in heart rate and oxygen uptake kinetics in type 2 diabetes patients, considering their cardiovascular medication. It was hypothesized that cardiovascular medication would affect heart rate and oxygen uptake kinetics and that this could be detected using a standardized exercise test. 18 subjects were tested for maximal oxygen uptake. Kinetics were measured in a single test session with standardized, randomized moderate-intensity work rate changes. Time series analysis was used to estimate kinetics. Greater maxima in cross-correlation functions indicate faster kinetics. 6 patients did not take any cardiovascular medication, 6 subjects took peripherally acting medication and 6 patients were treated with centrally acting medication. Maximum oxygen uptake was not significantly different between groups. Significant main effects were identified regarding differences in muscular oxygen uptake kinetics and heart rate kinetics. Muscular oxygen uptake kinetics were significantly faster than heart rate kinetics in the group with no cardiovascular medication (maximum in cross-correlation function of muscular oxygen uptake vs. heart rate; 0.32±0.08 vs. 0.25±0.06; p=0.001) and in the group taking peripherally acting medication (0.34±0.05 vs. 0.28±0.05; p=0.009) but not in the patients taking centrally acting medication (0.28±0.05 vs. 0.30±0.07; n.s.). It can be concluded that regulatory processes for the achievement of a similar maximal oxygen uptake are different between the groups. The used standardized test provided plausible results for heart rate and oxygen uptake kinetics in a single measurement session in this patient group. © Georg Thieme Verlag KG Stuttgart · New York.

  1. Phosphorus removal from aqueous solution in parent and aluminum-modified eggshells: thermodynamics and kinetics, adsorption mechanism, and diffusion process.

    Science.gov (United States)

    Guo, Ziyan; Li, Jiuhai; Guo, Zhaobing; Guo, Qingjun; Zhu, Bin

    2017-06-01

    Parent and aluminum-modified eggshells were prepared and characterized with X-ray diffraction, specific surface area measurements, infrared spectroscopy, zeta potential, and scanning electron microscope, respectively. Besides, phosphorus adsorptions in these two eggshells at different temperatures and solution pH were carried out to study adsorption thermodynamics and kinetics as well as the mechanisms of phosphorus adsorption and diffusion. The results indicated that high temperature was favorable for phosphorus adsorption in parent and aluminum-modified eggshells. Alkaline solution prompted phosphorus adsorption in parent eggshell, while the maximum adsorption amount was achievable at pH 4 in aluminum-modified eggshell. Adsorption isotherms of phosphorus in these eggshells could be well described by Langmuir and Freundlich models. Phosphorus adsorption amounts in aluminum-modified eggshell were markedly higher compared to those in parent eggshell. Adsorption heat indicated that phosphorus adsorption in parent eggshell was a typically physical adsorption process, while chemical adsorption mechanism of ion exchange between phosphorus and hydroxyl groups on the surface of eggshells was dominated in aluminum-modified eggshell. The time-resolved uptake curves showed phosphorus adsorption in aluminum-modified eggshell was significantly faster than that in parent eggshell. Moreover, there existed two clear steps in time-resolved uptake curves of phosphorus in parent eggshell. Based on pseudo-second order kinetic model and intraparticle diffusion model, we inferred more than one process affected phosphorus adsorption. The first process was the diffusion of phosphorus through water to external surface and the opening of pore channel in the eggshells, and the second process was mainly related to intraparticle diffusion.

  2. Kinetic and mechanistic investigations of the degradation of sulfamethazine in heat-activated persulfate oxidation process.

    Science.gov (United States)

    Fan, Yan; Ji, Yuefei; Kong, Deyang; Lu, Junhe; Zhou, Quansuo

    2015-12-30

    Sulfamethazine (SMZ) is widely used in livestock feeding and aquaculture as an antibiotic agent and growth promoter. Widespread occurrence of SMZ in surface water, groundwater, soil and sediment has been reported. In this study, degradation of SMZ by heat-activated persulfate (PS) oxidation was investigated in aqueous solution. Experimental results demonstrated that SMZ degradation followed pseudo-first-order reaction kinetics. The pseudo-first-order rate constant (kobs) was increased markedly with increasing concentration of PS and temperature. Radical scavenging tests revealed that the predominant oxidizing species was SO4·(-) with HO playing a less important role. Aniline moiety in SMZ molecule was confirmed to be the reactive site for SO4·(-) attack by comparison with substructural analogs. Nontarget natural water constituents affected SMZ removal significantly, e.g., Cl(-) and HCO3(-) improved the degradation while fulvic acid reduced it. Reaction products were enriched by solid phase extraction (SPE) and analyzed by liquid chromatography-electrospray ionization-triple quadrupole mass spectrometry (LC-ESI-MS/MS). 6 products derived from sulfonamide S--N bond cleavage, aniline moiety oxidation and Smiles-type rearrangement were identified, and transformation pathways of SMZ oxidation were proposed. Results reveal that heat-activated PS oxidation could be an efficient approach for remediation of water contaminated by SMZ and related sulfonamides. Copyright © 2015 Elsevier B.V. All rights reserved.

  3. Atomic-scale investigation of the interaction of organic molecules with MoS2-based hydrotreating model catalysts

    DEFF Research Database (Denmark)

    Salazar Moreira, Norberto José

    The aim of this work is to provide new insight into the formation, activation and reactivity of hydrotreating catalysts extensively used in the refinery for the conversion of heavy feedstocks and for improving the quality of the final oil products. This is done through numerous studies of the con......The aim of this work is to provide new insight into the formation, activation and reactivity of hydrotreating catalysts extensively used in the refinery for the conversion of heavy feedstocks and for improving the quality of the final oil products. This is done through numerous studies...... of the conversion of molybdenum oxides and metallic precursors into molybdenum disulfide (MoS2), the active phase involved in most of the hydrotreating reactions, especially for those dedicated to the removal of sulfur from various fuel fractions, commonly referred to as hydrodesulfurization (HDS). The evolution...... the presence of the reduced MoOx phase impedes the MoS2 growth and leads to rather stable amorphous oxysulfide phases. The sulfidation in H2S atmosphere of molybdenum metal and bimetallic cobalt-molybdenum clusters deposited on Au(111) facilitate instead the formation of well-dispersed MoS2 and Co-promoted Mo...

  4. Modulation of drug release kinetics of shellac-based matrix tablets by in-situ polymerization through annealing process.

    Science.gov (United States)

    Limmatvapirat, Sontaya; Limmatvapirat, Chutima; Puttipipatkhachorn, Satit; Nunthanid, Jurairat; Luangtana-anan, Manee; Sriamornsak, Pornsak

    2008-08-01

    A new oral-controlled release matrix tablet based on shellac polymer was designed and developed, using metronidazole (MZ) as a model drug. The shellac-based matrix tablets were prepared by wet granulation using different amounts of shellac and lactose. The effect of annealing temperature and pH of medium on drug release from matrix tablets was investigated. The increased amount of shellac and increased annealing temperature significantly affected the physical properties (i.e., tablet hardness and tablet disintegration) and MZ release from the matrix tablets. The in-situ polymerization played a major role on the changes in shellac properties during annealing process. Though the shellac did not dissolve in acid medium, the MZ release in 0.1N HCl was faster than in pH 7.3 buffer, resulting from a higher solubility of MZ in acid medium. The modulation of MZ release kinetics from shellac-based matrix tablets could be accomplished by varying the amount of shellac or annealing temperature. The release kinetics was shifted from relaxation-controlled release to diffusion-controlled release when the amount of shellac or the annealing temperature was increased.

  5. Kinetic Monte Carlo simulations for transient thermal fields: Computational methodology and application to the submicrosecond laser processes in implanted silicon.

    Science.gov (United States)

    Fisicaro, G; Pelaz, L; Lopez, P; La Magna, A

    2012-09-01

    Pulsed laser irradiation of damaged solids promotes ultrafast nonequilibrium kinetics, on the submicrosecond scale, leading to microscopic modifications of the material state. Reliable theoretical predictions of this evolution can be achieved only by simulating particle interactions in the presence of large and transient gradients of the thermal field. We propose a kinetic Monte Carlo (KMC) method for the simulation of damaged systems in the extremely far-from-equilibrium conditions caused by the laser irradiation. The reference systems are nonideal crystals containing point defect excesses, an order of magnitude larger than the equilibrium density, due to a preirradiation ion implantation process. The thermal and, eventual, melting problem is solved within the phase-field methodology, and the numerical solutions for the space- and time-dependent thermal field were then dynamically coupled to the KMC code. The formalism, implementation, and related tests of our computational code are discussed in detail. As an application example we analyze the evolution of the defect system caused by P ion implantation in Si under nanosecond pulsed irradiation. The simulation results suggest a significant annihilation of the implantation damage which can be well controlled by the laser fluence.

  6. Kinetics and energy efficiency for the degradation of 1,4-dioxane by electro-peroxone process

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Huijiao; Bakheet, Belal; Yuan, Shi; Li, Xiang; Yu, Gang [School of Environment, Tsinghua University, Beijing 100084 (China); Murayama, Seiichi [Power and Industrial Systems R& D Center, Toshiba Corporation, Fuchu-shi, Tokyo (Japan); Wang, Yujue, E-mail: wangyujue@tsinghua.edu.cn [School of Environment, Tsinghua University, Beijing 100084 (China)

    2015-08-30

    Highlights: • E-peroxone couples electrolysis with ozonation to driven peroxone reaction for pollutant degradation. • Significant amounts of ·OH can be efficiently produced in the E-peroxone process. • E-peroxone greatly enhances 1,4-dioxane degradation kinetics compared with ozonation and electrolysis. • E-peroxone consumes less energy for 1,4-dioxane mineralization than ozonation and electrolysis. • E-peroxone offers a cost-effective and energy-efficient alternative to degrade 1,4-dioxane. - Abstract: Degradation of 1,4-dioxane by ozonation, electrolysis, and their combined electro-peroxone (E-peroxone) process was investigated. The E-peroxone process used a carbon-polytetrafluorethylene cathode to electrocatalytically convert O{sub 2} in the sparged ozone generator effluent (O{sub 2} and O{sub 3} gas mixture) to H{sub 2}O{sub 2}. The electro-generated H{sub 2}O{sub 2} then react with sparged O{sub 3} to yield aqueous ·OH, which can in turn oxidize pollutants rapidly in the bulk solution. Using p-chlorobenzoic acid as ·OH probe, the pseudo-steady concentration of ·OH was determined to be ∼0.744 × 10{sup −9} mM in the E-peroxone process, which is approximately 10 and 186 times of that in ozonation and electrolysis using a Pt anode. Thanks to its higher ·OH concentration, the E-peroxone process eliminated 96.6% total organic carbon (TOC) from a 1,4-dioxane solution after 2 h treatment with a specific energy consumption (SEC) of 0.376 kWh g{sup −1} TOC{sub removed}. In comparison, ozonation and electrolysis using a boron-doped diamond anode removed only ∼6.1% and 26.9% TOC with SEC of 2.43 and 0.558 kWh g{sup −1} TOC{sub removed}, respectively. The results indicate that the E-peroxone process can significantly improve the kinetics and energy efficiency for 1,4-dioxane mineralization as compared to the two individual processes. The E-peroxone process may thus offer a highly effective and energy-efficient alternative to treat 1,4-dioxane

  7. A novel kinetic modeling method for the stabilization phase of the composting process for biodegradation of solid wastes.

    Science.gov (United States)

    Ebrahimzadeh, Reza; Ghazanfari Moghaddam, Ahmad; Sarcheshmehpour, Mehdi; Mortezapour, Hamid

    2017-12-01

    Biomass degradation kinetics of the composting process for kitchen waste, pruned elm tree branches and sheep manure were studied to model changes in volatile solids (VS) over time. Three experimental reactors containing raw mixtures with a carbon to nitrogen (C/N) ratio of 27:1 and a moisture content of 65% were prepared. During the composting process two of the reactors used forced air and the third used natural aeration. The composting stabilization phases in all reactors were completed in 30 days. During this period, composting indexes such as temperature, moisture content and VS changes were recorded. Elementary reactions were used for kinetics modeling of the degradation process. Results showed that the numerical values of rate constant ( k) for zero-order ranged from 0.86 to 1.03 VS×day -1 , for first-order models it ranged from 0.01 to 0.02 day -1 , for second-order the range was from 1.36×10 -5 to 1.78×10 -5 VS -1 ×day -1 and for n-order the rate constant ranged from 0.031 to 0.095 VS (1-n) ×day -1 . The resulting models were validated by comparing statistical parameters. Evaluation of the models showed that, in the aerated reactors, the n-order models (less than 1) successfully estimated the VS changes. In the non-aeration reactor, for the second-order model good agreement was achieved between the simulated and actual quantities of VS. Also, half-life time provided a useful criterion for the estimation of expected time for completion of different phases of composting.

  8. Effects of high-pressure process on kinetics of leaching oil from soybean powder using hexane in batch systems.

    Science.gov (United States)

    Uhm, Joo Tae; Yoon, Won Byong

    2011-08-01

    Mass transfer models of leaching oil from soybean (Glycine max) flour with hexane after high-pressure process (HPP) treatment were developed. High pressure (450 MPa) was applied to the soybean flour (mean diameter of flour particle: 365 μm) for 30 min before leaching the oil components in the solvent. The ratio of solvent (volume, mL) to soybean flour (mass, g), such as 1:10 and 1:20, was employed to characterize the effect of solvent ratio on the leaching rate in the batch type of extraction process. Ultraviolet absorbance at 300 nm was used to monitor the extraction rate. Saturation solubility (C(AS)) was determined to be 21.73 kg/m³. The mass transfer coefficients (k) were determined based on the 1st- and 2nd-order kinetic models. The 2nd kinetic model showed better fit. The HPP treatment showed a higher extraction rate and yield compared to the control, while the amount of solvent did not affect the extraction rate and yield. The scanning electron microscope showed that HPP-treated soybean particles included more pores than the untreated. The pores observed in the HPP-treated soybean flours might help increase the mass transfer rate of solvent and solute in the solid matrix. High-pressure processing can help increase the extraction rate of oil from the soybean flour operated in batch systems. The conventional solid to solvent ratio (1:20) used to extract oil composition from the plant seed did not help increase the amount of oil extracted from the soybean flour. © 2011 Institute of Food Technologists®

  9. Kinetic simulations of neoclassical and anomalous transport processes in helical systems

    International Nuclear Information System (INIS)

    Sugama, Hideo; Watanabe, Tomohiko; Nunami, Masanori; Satake, Shinsuke; Matsuoka, Seikichi; Tanaka, Kenji

    2012-01-01

    Drift kinetic and gyrokinetic theories and simulations are powerful means for quantitative predictions of neoclassical and anomalous transport fluxes in helical systems such as the Large Helical Device (LHD). The δf Monte Carlo particle simulation code, FORTEC-3D, is used to predict radial profiles of the neoclassical particle and heat transport fluxes and the radial electric field in helical systems. The radial electric field profiles in the LHD plasmas are calculated from the ambipolarity condition for the neoclassical particle fluxes obtained by the global simulations using the FORTEC-3D code, in which effects of ion or electron finite orbit widths are included. Gyrokinetic Vlasov simulations using the GKV code verify the theoretical prediction that the neoclassical optimization of helical magnetic configuration enhances the zonal flow generation which leads to the reduction of the turbulent heat diffusivity χ i due to the ion temperature gradient (ITG) turbulence. Comparisons between results for the high ion temperature LHD experiment and the gyrokinetic simulations using the GKV-X code show that the χ i profile and the poloidal wave number spectrum of the density fluctuation obtained from the simulations are in reasonable agreements with the experimental results. It is predicted theoretically and confirmed by the linear GKV simulations that the E × B rotation due to the background radial electric field E r can enhance the zonal-flow response to a given source. Thus, in helical systems, the turbulent transport is linked to the neoclassical transport through E r which is determined from the ambipolar condition for neoclassical particle fluxes and influences the zonal flow generation leading to reduction of the turbulent transport. In order to investigate the E r effect on the regulation of the turbulent transport by the zonal flow generation, the flux-tube bundle model is proposed as a new method for multiscale gyrokinetic simulations. (author)

  10. Kinetic Behavior of Aggregation-Exchange Growth Process with Catalyzed-Birth

    International Nuclear Information System (INIS)

    Han Anjia; Chen Yu; Lin Zhenquan; Ke Jianhong

    2007-01-01

    We propose an aggregation model of a two-species system to mimic the growth of cities' population and assets, in which irreversible coagulation reactions and exchange reactions occur between any two aggregates of the same species, and the monomer-birth reactions of one species occur by the catalysis of the other species. In the case with population-catalyzed birth of assets, the rate kernel of an asset aggregate B k of size k grows to become an aggregate B k+1 through a monomer-birth catalyzed by a population aggregate A j of size j is J(k,j) = Jkj λ . And in mutually catalyzed birth model, the birth rate kernels of population and assets are H(k,j) = Hkj η and J(k,j) = Jkj λ , respectively. The kinetics of the system is investigated based on the mean-field theory. In the model of population-catalyzed birth of assets, the long-time asymptotic behavior of the assets aggregate size distribution obeys the conventional or modified scaling form. In mutually catalyzed birth system, the asymptotic behaviors of population and assets obey the conventional scaling form in the case of η = λ = 0, and they obey the modified scaling form in the case of η = 0,λ = 1. In the case of η = λ = 1, the total mass of population aggregates and that of asset aggregates both grow much faster than those in population-catalyzed birth of assets model, and they approaches to infinite values in finite time.

  11. In situ photoemission spectroscopy using synchrotron radiation for O2 translational kinetic energy induced oxidation processes of partially-oxidized Si(001) surfaces

    International Nuclear Information System (INIS)

    Teraoka, Yuden; Yoshigoe, Akitaka

    2001-01-01

    The influence of translational kinetic energy of incident O 2 molecules for the passive oxidation process of partially-oxidized Si(001) surfaces has been studied by photoemission spectroscopy. The translational kinetic energy of O 2 molecules was controlled up to 3 eV by a supersonic seed beam technique using a high temperature nozzle. Two translational kinetic energy thresholds (1.0 eV and 2.6 eV) were found out in accordance with the first-principles calculation for the oxidation of clean surfaces. Si-2p photoemission spectra measured in representative translational kinetic energies revealed that the translational kinetic energy dependent oxidation of dimers and the second layer (subsurface) backbonds were caused by the direct dissociative chemisorption of O 2 molecules. Moreover, the difference in chemical bonds for oxygen atoms was found out to be as low and high binding energy components in O-1s photoemission spectra. Especially, the low binding energy component increased with increasing the translational kinetic energy that indicates the translational kinetic energy induced oxidation in backbonds. (author)

  12. CO2 capture using aqueous ammonia: kinetic study and process simulation

    DEFF Research Database (Denmark)

    Darde, Victor Camille Alfred; van Well, Willy J.M.; Stenby, Erling Halfdan

    2011-01-01

    to 0.6. The results were compared with those found for 30 wt% mono-ethanolamine (MEA) solutions.The capture process was simulated successfully using the simulator Aspen Plus coupled with the extended UNIQUAC thermodynamic model available for the NH3–CO2–H2O system. For this purpose, a user model......Carbon dioxide capture using aqueous ammonia is a post-combustion technology that has shown a good potential. Therefore this process is studied by measuring the rate of absorption of carbon dioxide by aqueous ammonia and by performing process simulation. The rate of absorption of carbon dioxide...

  13. Some kinetic and spectroscopic evidence on intramolecular relaxation processes in polyatomic molecules

    International Nuclear Information System (INIS)

    Quack, M.

    1983-01-01

    The description and definition of intramolecular vibrational relaxation processes is discussed within the framework of the quantum mechanical and statistical mechanical equations of motion. The evidence from quite different experimental sources is summarized under the common aspect of vibrational relaxation. Although much of the evidence remains ambiguous, there is good indication that a localized vibrational excitation relaxes typically in 0.1 to 10 picoseconds, which is long compared to many optical and reactive processes

  14. Kinetic-quantum chemical model for catalytic cycles: the Haber-Bosch process and the effect of reagent concentration.

    Science.gov (United States)

    Kozuch, Sebastian; Shaik, Sason

    2008-07-03

    A combined kinetic-quantum chemical model is developed with the goal of estimating in a straightforward way the turnover frequency (TOF) of catalytic cycles, based on the state energies obtained by quantum chemical calculations. We describe how the apparent activation energy of the whole cycle, so-called energetic span (delta E), is influenced by the energy levels of two species: the TOF determining transition state (TDTS) and the TOF determining intermediate (TDI). Because these key species need not be adjoining states, we conclude that for catalysis there are no rate-determining steps, only rate determining states. In addition, we add here the influence of reactants concentrations. And, finally, the model is applied to the Haber-Bosch process of ammonia synthesis, for which we show how to calculate which catalyst will be the most effective under specific reagents conditions.

  15. Kinetics and evolved gas analysis for pyrolysis of food processing wastes using TGA/MS/FT-IR.

    Science.gov (United States)

    Özsin, Gamzenur; Pütün, Ayşe Eren

    2017-06-01

    The objective of this study was to identify the pyrolysis of different bio-waste produced by food processing industry in a comprehensible manner. For this purpose, pyrolysis behaviors of chestnut shells (CNS), cherry stones (CS) and grape seeds (GS) were investigated by thermogravimetric analysis (TGA) combined with a Fourier-transform infrared (FT-IR) spectrometer and a mass spectrometer (MS). In order to make available theoretical groundwork for biomass pyrolysis, activation energies were calculated with the help of four different model-free kinetic methods. The results are attributed to the complex reaction schemes which imply parallel, competitive and complex reactions during pyrolysis. During pyrolysis, the evolution of volatiles was also characterized by FT-IR and MS. The main evolved gases were determined as H 2 O, CO 2 and hydrocarbons such as CH 4 and temperature dependent profiles of the species were obtained. Copyright © 2017 Elsevier Ltd. All rights reserved.

  16. Removal of Dye (Blue 56 From Aqueous Solution via Adsorption onto Pistachio Shell: kinetic and isotherm study of removal process

    Directory of Open Access Journals (Sweden)

    A. Ravanpaykar

    2012-03-01

    Full Text Available In the present investigation, shells of pistachio are used as adsorbents and they have been successfully used for the removal of Blue 56, from water samples. The effect of various parameters such as: pH, amounts of adsorbents, size of adsorbent particles and contact time on removal processing were investigated. Inthisstudy Freundlichabsorptionisotherms and Langmuir were investigated. The experimental data were correlated reasonably well by the Freundlich adsorption isotherm and isotherm parameters were calculated. In order to investigate the efficiency of Blue 56 adsorption on the pistachio shell, pseudo-first-order, pseudo-second-order, Elovich and intra-particle diffusion kinetic models were studied. Themodel that hadgoodcorrelationtoattractFreundlichwas chosenasthemodel. Its kineticsfollowsthepseudosecond order reaction.

  17. Pile noise experiment in MINERVE reactor to estimate kinetic parameters using various data processing methods

    Energy Technology Data Exchange (ETDEWEB)

    Geslot, Benoit; Gruel, Adrien; Pepino, Alexandra; Di Salvo, Jacques; Izarra, Gregoire de; Jammes, Christian; Destouches, Christophe; Blaise, Patrick [CEA, DEN, DER/SPEx, Cadarache, F-13108 St Paul Lez Durance (France)

    2015-07-01

    MINERVE is a two-zone pool type zero power reactor operated by CEA (Cadarache, France). Kinetic parameters of the core (prompt neutron decay constant, delayed neutron fraction, generation time) have been recently measured using various pile noise experimental techniques, namely Feynman-α, Rossi-α and Cohn-α. Results are discussed and compared to each other's. The measurement campaign has been conducted in the framework of a tri-partite collaboration between CEA, SCK.CEN and PSI. Results presented in this paper were obtained thanks to a time-stamping acquisition system developed by CEA. PSI performed simultaneous measurements which are presented in a companion paper. Signals come from two high efficiency fission chambers located in the graphite reflector next to the core driver zone. Experiments were conducted at critical state with a reactor power of 0.2 W. The core integral fission rate is obtained from a calibrated miniature fission chamber located at the center of the core. Other results obtained in two sub-critical configurations will be presented elsewhere. Best estimate delayed neutron fraction comes from the Cohn-α method: 747 ± 15 pcm (1σ). In this case, the prompt decay constant is 79 ± 0.5 s{sup -1} and the generation time is 94.5 ± 0.7 μs. Other methods give consistent results within the confidence intervals. Experimental results are compared to calculated values obtained from a full 3D core modeling with the CEA-developed Monte Carlo code TRIPOLI4.9 associated with its continuous energy JEFF3.1.1-based library. A very good agreement is observed for the calculated delayed neutron fraction (748.7 ± 0.4 pcm at 1σ), that is a difference of -0.3% with the experiment. On the contrary, a 10% discrepancy is observed for the calculated generation time (104.4 ± 0.1 μs at 1σ). (authors)

  18. Modelling Chemical Kinetics of Soybean Oil Transesterification Process for Biodiesel Production: An Analysis of Molar Ratio between Alcohol and Soybean Oil Temperature Changes on the Process Conversion Rate

    Directory of Open Access Journals (Sweden)

    Maicon Tait

    2006-12-01

    Full Text Available A mathematical model describing chemical kinetics of transesterification of soybean oil for biodiesel production has been developed. The model is based on the reverse mechanism of transesterification reactions and describes dynamics concentration changes of triglycerides, diglycerides, monoglycerides, biodiesel, and glycerol production. Reaction rate constants were written in the Arrhenius form. An analysis of key process variables such as temperature and molar ratio soybean oil- alcohol using response surface analysis was performed to achieve the maximum soybean conversion rate to biodiesel. The predictive power of the developed model was checked for the very wide range of operational conditions and parameters values by fitting different experimental results for homogeneous catalytic and non-catalytic processes published in the literature. A very good correlation between model simulations and experimental data was observed.

  19. Kinetics and mechanism of the biodegradation of PLA/clay nanocomposites during thermophilic phase of composting process.

    Science.gov (United States)

    Stloukal, Petr; Pekařová, Silvie; Kalendova, Alena; Mattausch, Hannelore; Laske, Stephan; Holzer, Clemens; Chitu, Livia; Bodner, Sabine; Maier, Guenther; Slouf, Miroslav; Koutny, Marek

    2015-08-01

    The degradation mechanism and kinetics of polylactic acid (PLA) nanocomposite films, containing various commercially available native or organo-modified montmorillonites (MMT) prepared by melt blending, were studied under composting conditions in thermophilic phase of process and during abiotic hydrolysis and compared to the pure polymer. Described first order kinetic models were applied on the data from individual experiments by using non-linear regression procedures to calculate parameters characterizing aerobic composting and abiotic hydrolysis, such as carbon mineralization, hydrolysis rate constants and the length of lag phase. The study showed that the addition of nanoclay enhanced the biodegradation of PLA nanocomposites under composting conditions, when compared with pure PLA, particularly by shortening the lag phase at the beginning of the process. Whereas the lag phase of pure PLA was observed within 27days, the onset of CO2 evolution for PLA with native MMT was detected after just 20days, and from 13 to 16days for PLA with organo-modified MMT. Similarly, the hydrolysis rate constants determined tended to be higher for PLA with organo-modified MMT, particularly for the sample PLA-10A with fastest degradation, in comparison with pure PLA. The acceleration of chain scission in PLA with nanoclays was confirmed by determining the resultant rate constants for the hydrolytical chain scission. The critical molecular weight for the hydrolysis of PLA was observed to be higher than the critical molecular weight for onset of PLA mineralization, suggesting that PLA chains must be further shortened so as to be assimilated by microorganisms. In conclusion, MMT fillers do not represent an obstacle to acceptance of the investigated materials in composting facilities. Copyright © 2015 Elsevier Ltd. All rights reserved.

  20. Kinetics of varnish long-term drying process monitored by a heterogeneous optical sensor system

    International Nuclear Information System (INIS)

    Saccon, F A M; De Oliveira, F M D R; Ribas, M O; Zambianchi, P Jr; Muller, M; Fabris, J L

    2013-01-01

    The drying process of an acrylic varnish film was monitored over 24 h by a heterogeneous optical sensor system. The system employs a fibre optic transducer based on Bragg gratings and optical coherence tomography, operating respectively around 1.55 and 1.3 µm. The sensor is able to provide information about the temporal evolution of temperature, mechanical deformation, thickness and average refractive index of the coating during the drying process. Resolutions for these optically measured parameters are 0.05 °C (temperature), 0.5 µε (strain), 1.5 µm (thickness) and 0.004 (refractive index). Besides, the sensor can detect the growth of a surface dry skin and supply information about the film bulk uniformity. A model for the mass loss of solvent as the drying process evolves is also discussed. (paper)

  1. Coarse-grained stochastic processes and kinetic Monte Carlo simulators for the diffusion of interacting particles

    Science.gov (United States)

    Katsoulakis, Markos A.; Vlachos, Dionisios G.

    2003-11-01

    We derive a hierarchy of successively coarse-grained stochastic processes and associated coarse-grained Monte Carlo (CGMC) algorithms directly from the microscopic processes as approximations in larger length scales for the case of diffusion of interacting particles on a lattice. This hierarchy of models spans length scales between microscopic and mesoscopic, satisfies a detailed balance, and gives self-consistent fluctuation mechanisms whose noise is asymptotically identical to the microscopic MC. Rigorous, detailed asymptotics justify and clarify these connections. Gradient continuous time microscopic MC and CGMC simulations are compared under far from equilibrium conditions to illustrate the validity of our theory and delineate the errors obtained by rigorous asymptotics. Information theory estimates are employed for the first time to provide rigorous error estimates between the solutions of microscopic MC and CGMC, describing the loss of information during the coarse-graining process. Simulations under periodic boundary conditions are used to verify the information theory error estimates. It is shown that coarse-graining in space leads also to coarse-graining in time by q2, where q is the level of coarse-graining, and overcomes in part the hydrodynamic slowdown. Operation counting and CGMC simulations demonstrate significant CPU savings in continuous time MC simulations that vary from q3 for short potentials to q4 for long potentials. Finally, connections of the new coarse-grained stochastic processes to stochastic mesoscopic and Cahn-Hilliard-Cook models are made.

  2. Kinetic study of Saponins B stability in navy beans under different processing conditions

    Science.gov (United States)

    Saponins are rich in the legumes which are known to provide many health benefits for human beings. Saponins B is the main component in the saponins group present in navy beans. The stability of saponins B during food processing is a key issue to evaluating the quality and nutrition of food products....

  3. Two-Nozzle Flame Spray Pyrolysis (FSP) Synthesis of CoMo/Al2O3 Hydrotreating Catalysts

    DEFF Research Database (Denmark)

    Høj, Martin; Pham, David K.; Brorson, Michael

    2013-01-01

    and the hydrodenitrogenation activity improved from 70 to 90 % relative activity. This suggests that better promotion of the active molybdenum sulfide phase was achieved when using two-nozzle FSP synthesis, probably due to less formation of the undesired phase CoAl2O4, which makes Co unavailable for promotion.......Two-nozzle frame spray analysis (FSP) synthesis of CoMo/Al2O3 where Co and Al are sprayed in separate flames was applied to minimize the formation of CoAl2O4 observed in one-nozzle flame spray pyrolysis (FSP) synthesis and the materials were characterized by N2-adsorption (BET), X-ray diffraction...... (XRD), UV–vis diffuse reflectance spectroscopy, Raman spectroscopy, transmission electron microscopy, and catalytic performances in hydrotreating. By varying the flame mixing distances (81–175 mm) the amount of CoAl2O4 could be minimized. As evidenced by UV–vis spectroscopy, CoAl2O4 was detected only...

  4. Alternatives for recovering metals from spent catalysts for hydrotreating of heavy hydrocarbons: a case study; Alternativas para la recuperacion de metales a partir de catalizadores gastados del hidrotratamiento de hidrocarburos pesados: un caso de estudio

    Energy Technology Data Exchange (ETDEWEB)

    Alonso, Fernando; Ramirez, Sergio; Ancheyta, Jorge; Mavil, Martha [Instituto Mexicano del Petroleo, Mexico, D.F. (Mexico)]. E-mail: jancheyt@imp.mx

    2008-05-15

    The increasing production of spent hydrotreating catalysts used for processing heavy hydrocarbons and the problems related to their disposal are described in this work. These catalysts contain important amounts of heavy metals such as molybdenum (Mo), nickel (Ni), cobalt (Co) and vanadium (V), which can be recovered and hence an economical benefit may be obtained. The results of experimental tests for alkaline leaching (NaOH) to recover V and Mo, and the effect of operating conditions on metal recovery are also presented. The results show that, in general, the highest recovery of Mo is obtained at pH 8.5 and leaching time of 12 hours, while in the case of V, the highest recovery is observed at pH 9.0 and 8 hours. In both cases, the leaching solution contained 10 wt % alkaline. Based on the experimental information and data from a commercial plant, a preliminary economy study was developed, in which the expected economical benefits of metals recovery from spent catalysts used for hydrotreating heavy hydrocarbon are estimated. [Spanish] En el presente trabajo se describe la problematica de la creciente produccion de catalizadores gastados de los procesos de hidrotratamiento de hidrocarburos pesados. Estos catalizadores contienen cantidades importantes de metales pesados como molibdeno (Mo), niquel (Ni), cobalto (Co) y vanadio (V), que son susceptibles de recuperarse y obtener con ello un beneficio economico. Tambien se presentan resultados de pruebas experimentales de lixiviacion alcalina (NaOH) para la recuperacion de V y Mo, y el efecto de las variables de operacion sobre la recuperacion de metales. En general, se encontro que las mejores recuperaciones de Mo fueron a pH de 8.5 y 12 h, mientras que para el V fueron a pH de 9.0 y 8 h, ambos a una concentracion del agente lixiviante de 10% en peso. Con base en la informacion experimental obtenida y datos de una planta industrial se presenta un estudio economico preliminar, en el que se estiman los beneficios

  5. Dissipation kinetics of beta-cyfluthrin and imidacloprid in tea and their transfer from processed tea to infusion.

    Science.gov (United States)

    Paramasivam, M; Deepa, M; Selvi, C; Chandrasekaran, S

    2017-10-01

    Dissipation kinetics of mixed formulation consisting beta-cyfluthrin and imidacloprid in tea crop under an open field ecosystem was investigated. The mixed formulation was applied on tea plant at recommended (27 + 63) and double the recommended (54 + 126g a.i./ha) dose and residues were determined using gas chromatography-electron capture detector and high performance liquid chromatography-photodiode array detector for beta-cyfluthrin and imidacloprid, respectively. The limit of quantification of analytical method was 0.05µg/g and the average recoveries were ranged from 88.36% to 103.49% with relative standard deviations of less than 6% at three spiked levels. The experimental results showed that in the green tea leaves imidacloprid dissipated faster than beta-cyfluthrin with the half-life ranging between 1.20-1.39 and 2.89-3.15days, respectively. The beta-cyfluthrin residues present in the processed tea not transferred into the tea infusion during the infusion process and imidacloprid transferred in the range 43.12-49.7%. On the basis of the transfer of residues from processed tea to infusion, a waiting period of 17 days for tea plucking after pesticide application at recommended dose may be suggested. Copyright © 2017 Elsevier Inc. All rights reserved.

  6. Kinetic particularities of strained alicyclic compounds formation in catalytic methanol to hydrocarbon transformation process

    OpenAIRE

    Doluda V.; Brovko R.; Giniatullina N.; Sulman M.

    2017-01-01

    The catalytic transformation of methanol into hydrocarbons is a complex chemical process, accompanied by chain parallel chemical transformation reactions. The most valuable products of the methanol to hydrocarbons catalytic transformation reaction are the strained hydrocarbons — cyclopropane derivatives. These compounds can be used as a high-energy fuel, and also as a valuable chemical raw material. However, the yield of strained compounds in methanol to hydrocarbons catalytic transformation ...

  7. Spray Drying Processing: granules production and drying kinetics of droplets; El proceso de secado por atomizacion: formacion de granulos y cinetica de secado de gotas

    Energy Technology Data Exchange (ETDEWEB)

    Mondragon, R.; Julia, J. E.; Barba, A.; Jarque, J. C.

    2013-09-01

    Spray drying is a unit operation very common in many industrial processes. For each particular application, the resulting granulated material must possess determined properties that depend on the conditions in which the spray drying processing has been carried out, and whose dependence must be known in order to optimize the quality of the material obtained. The large number of variables that influence on the processes of matter and energy transfer and on the formation of granular material has required a detailed analysis of the drying process. Over the years there have been many studies on the spray drying processing of all kind of materials and the influence of process variables on the drying kinetics of the granulated material properties obtained. This article lists the most important works published for both the spray drying processing and the drying of individual droplets, as well as studies aimed at modeling the drying kinetics of drops. (Author)

  8. Extension of the principles of the kinetic conception of strength to the process of spalling fracture

    International Nuclear Information System (INIS)

    Molodets, A.M.; Dremin, A.N.

    1983-01-01

    The universality and graphical physical meaning of the characteristic relationship for thermal activation processes and time stimulate attempts for its utilization to describe the time dependence of the spall strength. The involvement of this relationship to describe spall requires a definite model of the spall process first. It is also necessary to to consider the question of the relationship between the applied and local stresses and the selection of a definite connection between these variables. The phenomenological model of spall in which the analogue of the cumulative rudimentary discontinuity is isolated has already been proposed. In this paper, a model is proposed within the framework of this previously described model, taking into account the thermal activation processes and the mean level of the stresses. Comparisons of this model with experimental data on the spall in copper show good agreement. In the spall domain the overstress factor is approximately one third its limit value. This means that higher values of the applied stresses than those found under quasistatic conditions correspond to the identical local stress level. It is possible that the thermal activation stage proceeds during spall in metals exactly as under quasistatic conditions, namely; rudimentary discontinuities are submicrocracks of dimensions less than 10 -7 microns

  9. Effects of methanol on lipases: molecular, kinetic and process issues in the production of biodiesel.

    Science.gov (United States)

    Lotti, Marina; Pleiss, Jürgen; Valero, Francisco; Ferrer, Pau

    2015-01-01

    The biotechnological production of biodiesel is based on transesterification/esterification reactions between a source of fatty acids and a short-chain alcohol, usually methanol, catalysed by enzymes belonging to the class known as lipases. Several lipases used in industrial processes, although stable in the presence of other organic solvents, are inactivated by methanol at or below the concentration optimal for biodiesel production, making it necessary to use stepwise methanol feeding or pre-treatment of the enzyme. In this review article we focus on what is currently know about methanol inactivation of lipases, a phenomenon which is not common to all lipase enzymes, with the goal of improving the biocatalytic process. We suggest that different mechanisms can lead to inactivation of different lipases, in particular substrate inhibition and protein unfolding. Attempts to improve the performances of methanol sensitive lipases by mutagenesis as well as process engineering approaches are also summarized. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Analysis of the kinetics of decohesion process in the conditions of cyclic temperature variations

    International Nuclear Information System (INIS)

    Zuchowski, R.

    1981-01-01

    Specimens made of four types of heat-resistant steels were used in the investigation. Various variants of loading process were applied, resulting in thermal fatigue, cyclic creep and isothermal fatigue. Stress or strain variation as well as intensity of acoustic emission were recorded during the tests as a function of time. Cyclic variations of strain or stress amplitude were found to occur one full period covering few to several cycles. Comparing the relative number of acoustic emission impulses with the variation of stress or strain leads to the conclusion that cyclic character of strain or stress variation results from cyclic character of damage cumulation process. This statement is confirmed by the results of material damage degree determination based on specific strain work measurements. Results of investigation testify to the equivalence of action (in terms of energy) of cyclically variable force field at constant temperature and of constant force field in the conditions of cyclic temperature variations. Damage mechanism can be different in each case, because it depends (for a given material) on loading process parameters and in particular - on temperature and stress value. (orig./HP)

  11. Fuel processing for PEM fuel cells: transport and kinetic issues of system design

    Science.gov (United States)

    Zalc, J. M.; Löffler, D. G.

    In light of the distribution and storage issues associated with hydrogen, efficient on-board fuel processing will be a significant factor in the implementation of PEM fuel cells for automotive applications. Here, we apply basic chemical engineering principles to gain insight into the factors that limit performance in each component of a fuel processor. A system consisting of a plate reactor steam reformer, water-gas shift unit, and preferential oxidation reactor is used as a case study. It is found that for a steam reformer based on catalyst-coated foils, mass transfer from the bulk gas to the catalyst surface is the limiting process. The water-gas shift reactor is expected to be the largest component of the fuel processor and is limited by intrinsic catalyst activity, while a successful preferential oxidation unit depends on strict temperature control in order to minimize parasitic hydrogen oxidation. This stepwise approach of sequentially eliminating rate-limiting processes can be used to identify possible means of performance enhancement in a broad range of applications.

  12. Combining Experiments and Simulations of Extraction Kinetics and Thermodynamics in Advanced Separation Processes for Used Nuclear Fuel

    Energy Technology Data Exchange (ETDEWEB)

    Nilsson, Mikael

    2018-05-15

    This 3-year project was a collaboration between University of California Irvine (UC Irvine), Pacific Northwest National Laboratory (PNNL), Idaho National Laboratory (INL), Argonne National Laboratory (ANL) and with an international collaborator at ForschungZentrum Jülich (FZJ). The project was led from UC Irvine under the direction of Profs. Mikael Nilsson and Hung Nguyen. The leads at PNNL, INL, ANL and FZJ were Dr. Liem Dang, Dr. Peter Zalupski, Dr. Nathaniel Hoyt and Dr. Giuseppe Modolo, respectively. Involved in this project at UC Irvine were three full time PhD graduate students, Tro Babikian, Ted Yoo, and Quynh Vo, and one MS student, Alba Font Bosch. The overall objective of this project was to study how the kinetics and thermodynamics of metal ion extraction can be described by molecular dynamic (MD) simulations and how the simulations can be validated by experimental data. Furthermore, the project includes the applied separation by testing the extraction systems in a single stage annular centrifugal contactor and coupling the experimental data with computational fluid dynamic (CFD) simulations. Specific objectives of the proposed research were: 1. Study and establish a rigorous connection between MD simulations based on polarizable force fields and extraction thermodynamic and kinetic data. 2. Compare and validate CFD simulations of extraction processes for An/Ln separation using different sizes (and types) of annular centrifugal contactors. 3. Provide a theoretical/simulation and experimental base for scale-up of batch-wise extraction to continuous contactors. We approached objective 1 and 2 in parallel. For objective 1 we started by studying a well established extraction system with a relatively simple extraction mechanism, namely tributyl phosphate. What we found was that well optimized simulations can inform experiments and new information on TBP behavior was presented in this project, as well be discussed below. The second objective proved a larger

  13. Isotherm and kinetic studies on adsorption of oil sands process-affected water organic compounds using granular activated carbon.

    Science.gov (United States)

    Islam, Md Shahinoor; McPhedran, Kerry N; Messele, Selamawit A; Liu, Yang; Gamal El-Din, Mohamed

    2018-07-01

    The production of oil from oil sands in northern Alberta has led to the generation of large volumes of oil sands process-affected water (OSPW) that was reported to be toxic to aquatic and other living organisms. The toxicity of OSPW has been attributed to the complex nature of OSPW matrix including the inorganic and organic compounds primarily naphthenic acids (NAs: C n H 2n+Z O x ). In the present study, granular activated carbon (GAC) adsorption was investigated for its potential use to treat raw and ozonated OSPW. The results indicated that NA species removal increased with carbon number (n) for a fixed Z number; however, the NA species removal decreased with Z number for a fixed carbon number. The maximum adsorption capacities obtained from Langmuir adsorption isotherm based on acid-extractable fraction (AEF) and NAs were 98.5 mg and 60.9 mg AEF/g GAC and 60 mg and 37 mg NA/g GAC for raw and ozonated OSPW, respectively. It was found that the Freundlich isotherm model best fits the AEF and NA equilibrium data (r 2  ≥ 0.88). The adsorption kinetics showed that the pseudo-second order and intraparticle diffusion models were both appropriate in modeling the adsorption kinetics of AEF and NAs to GAC (r 2  ≥ 0.97). Although pore diffusion was the rate limiting step, film diffusion was still significant for assessing the rate of diffusion of NAs. This study could be helpful to model, design and optimize the adsorption treatment technologies of OSPW and to assess the performance of other adsorbents. Copyright © 2018 Elsevier Ltd. All rights reserved.

  14. Chemical kinetics and transport processes in supercritical fluid extraction of coal. Final report, August 10, 1990--December 30, 1992

    Energy Technology Data Exchange (ETDEWEB)

    McCoy, B.J.; Smith, J.M.; Wang, M.; Zhang, C.J.

    1993-02-01

    The overall objective of this project was to study the supercritical fluid extraction of hydrocarbons from coal. Beyond the practical concern of deriving products from coal, the research has provided insights into the structure, properties, and reactivities of coal. Information on engineering fundamentals of coal thermolysis and extraction, including physical and chemical processes, is presented in this final report. To accomplish the goals of the project we developed continuous-flow experiments for fixed-bed samples of coal that allow two types of analysis of the extract: continuous spectrophotometric absorbance measurements of the lumped concentration of extract, and chromatographic determinations of molecular-weight distributions as a function of time. Thermolysis of coal yields a complex mixture of many extract products whose molecular-weight distribution (MWD) varies with time for continuous-flow, semibatch experiments. The flow reactor with a differential, fixed bed of coal particles contacted by supercritical t-butanol was employed to provide dynamic MWD data by means of HPLC gel permeation chromatography of the extract. The experimental results, time-dependent MWDs of extract molecules, were interpreted by a novel mathematical model based on continuous-mixture kinetics for thermal cleavage of chemical bonds in the coal network. The parameters for the MWDs of extractable groups in the coal and the rate constants for one- and two-fragment reaction are determined from the experimental data. The significant effect of temperature on the kinetics of the extraction was explained in terms of one- and two-fragment reactions in the coal.

  15. Oxidation of adsorbed ferrous iron: kinetics and influence of process conditions.

    Science.gov (United States)

    Buamah, R; Petrusevski, B; Schippers, J C

    2009-01-01

    For the removal of iron from groundwater, aeration followed with rapid (sand) filtration is frequently applied. Iron removal in this process is achieved through oxidation of Fe(2 + ) in aqueous solution followed by floc formation as well as adsorption of Fe(2 + ) onto the filter media. The rate of oxidation of the adsorbed Fe(2 + ) on the filter media plays an important role in this removal process. This study focuses on investigating the effect of pH on the rate of oxidation of adsorbed Fe(2 + ). Fe(2 + ) has been adsorbed, under anoxic conditions, on iron oxide coated sand (IOCS) in a short filter column and subsequently oxidized by feeding the column with aerated water. Ferrous ions adsorbed at pH 5, 6, 7 and 8 demonstrated consumption of oxygen, when aerated water was fed into the column. The oxygen uptake at pH 7 and 8 was faster than at pH 5 and 6. However the difference was less pronounced than expected. The difference is attributed to the pH buffering effect of the IOCS. At feedwater pH 5, 6 and 7 the pH in the effluent was higher than in the influent, while a pH drop should occur because of oxidation of adsorbed Fe(2 + ). At pH 8, the pH dropped. These phenomena are attributed to the presence of calcium and /or ferrous carbonate in IOCS.

  16. Application of the Marcus theory to description of the kinetics of reduction processes of organic cations

    International Nuclear Information System (INIS)

    Bogillo, V.I.; Lobanov, V.V.; Gragerov, I.P.

    1987-01-01

    The calculation of the rate constants for the processes in the reduction of diazonium, tropylium, verdazylium, and pyrylium cations by various organic electron donors, using the equations of the Marcus theory with allowance for the reorganization energy of only the outer coordination sphere, leads to values which are one to seven orders of magnitude higher than the experimental values. By quantum-chemical calculations it was shown that the reduction of diazonium and tropylium cations to the corresponding radicals is accompanied by a substantial change in the structure of the reagents. This leads to high values for the reorganization energy of the inner coordination sphere of the cations, which must be taken into account during calculation of the rate constants. The differences in the rate constants of the processes of direct electron transfer from the electron donors to the organic cations and the recombination of these reagents depend on the dissociation energy of the bond of the cation with the donor leading to the electron transfer products

  17. E-cadherin junction formation involves an active kinetic nucleation process

    Science.gov (United States)

    Biswas, Kabir H.; Hartman, Kevin L.; Yu, Cheng-han; Harrison, Oliver J.; Song, Hang; Smith, Adam W.; Huang, William Y. C.; Lin, Wan-Chen; Guo, Zhenhuan; Padmanabhan, Anup; Troyanovsky, Sergey M.; Dustin, Michael L.; Shapiro, Lawrence; Honig, Barry; Zaidel-Bar, Ronen; Groves, Jay T.

    2015-01-01

    Epithelial (E)-cadherin-mediated cell−cell junctions play important roles in the development and maintenance of tissue structure in multicellular organisms. E-cadherin adhesion is thus a key element of the cellular microenvironment that provides both mechanical and biochemical signaling inputs. Here, we report in vitro reconstitution of junction-like structures between native E-cadherin in living cells and the extracellular domain of E-cadherin (E-cad-ECD) in a supported membrane. Junction formation in this hybrid live cell-supported membrane configuration requires both active processes within the living cell and a supported membrane with low E-cad-ECD mobility. The hybrid junctions recruit α-catenin and exhibit remodeled cortical actin. Observations suggest that the initial stages of junction formation in this hybrid system depend on the trans but not the cis interactions between E-cadherin molecules, and proceed via a nucleation process in which protrusion and retraction of filopodia play a key role. PMID:26290581

  18. A KIND OF FLUORESCENCE PROBE TO STUDY THE KINETICS OF POLYMERIZATION PROCESS

    Institute of Scientific and Technical Information of China (English)

    YANG Guoqiang; WU Shikang

    1994-01-01

    Fluorescence properties of 1-phenyl-3-(4'-nitrophenyl) pyrazoline (PNP) were studied in bulk polymerization process of methylmethacrylate (MMA). The fluorescence intensity of PNP was enhanced and the emission maximum was blue shifted with the polymerization progress. In the period of auto-acceleration of the polymerization the enhancement of fluorescence intensity and blue shift of peak wavelength in spectra could be observed evidently. This means that the solvatochromic properties of PNP are influenced not only by the solvent polarity but also by the viscosity of the medium(especially by the phase transition). In solid state PNP emits from the charge transfer excited state without solvent relaxation. The transient emission spectra and the results from Bakhshiev model of solvent relaxation coincide with that from the polymerization experiment.

  19. Synthesis and crystal kinetics of cerium oxide nanocrystallites prepared by co-precipitation process

    International Nuclear Information System (INIS)

    Shih, C.J.; Chen, Y.J.; Hon, M.H.

    2010-01-01

    Cerium oxide nanocrystallites were synthesized at a relatively low temperature using cerium nitrate as starting materials in a water solution by a co-precipitation process. Effect of calcination temperature on the crystallite growth of cerium oxide nano-powders was investigated by X-ray diffraction, transmission electron microscopy and electron diffraction. The crystallization temperature of the cerium oxide powders was estimated to be about 273 K by XRD analysis. When calcined from 473 to 1273 K, the crystallization of the face-centered cubic phase was observed by XRD. The crystallite size of the cerium oxide increased from 10.0 to 43.8 nm with calcining temperature increasing from 673 to 1273 K. The activation energy for growth of cerium oxide nanoparticles was found to be 16.0 kJ mol -1 .

  20. Synthesis and crystal kinetics of cerium oxide nanocrystallites prepared by co-precipitation process

    Energy Technology Data Exchange (ETDEWEB)

    Shih, C.J., E-mail: cjshih@kmu.edu.tw [Department of Fragrance and Cosmetics Science, Kaohsiung Medical University, 100 Shi-Chuan 1st Road, Kaohsiung 807, Taiwan (China); Chen, Y.J. [Institute of Biomedical Sciences, National Sun Yat-Sen University, Kaohsiung 804, Taiwan (China); Hon, M.H. [Department of Materials Science and Engineering, National Cheng Kung University, Tainan 701, Taiwan (China)

    2010-05-15

    Cerium oxide nanocrystallites were synthesized at a relatively low temperature using cerium nitrate as starting materials in a water solution by a co-precipitation process. Effect of calcination temperature on the crystallite growth of cerium oxide nano-powders was investigated by X-ray diffraction, transmission electron microscopy and electron diffraction. The crystallization temperature of the cerium oxide powders was estimated to be about 273 K by XRD analysis. When calcined from 473 to 1273 K, the crystallization of the face-centered cubic phase was observed by XRD. The crystallite size of the cerium oxide increased from 10.0 to 43.8 nm with calcining temperature increasing from 673 to 1273 K. The activation energy for growth of cerium oxide nanoparticles was found to be 16.0 kJ mol{sup -1}.

  1. Treatment of statin compounds by advanced oxidation processes: Kinetic considerations and destruction mechanisms

    Science.gov (United States)

    Razavi, Behnaz; Song, Weihua; Santoke, Hanoz; Cooper, William J.

    2011-03-01

    This study examined the use of advanced oxidation/reduction processes (AO/RPs) for the destruction of cholesterol lowering statin pharmaceuticals. AO/RPs which utilize the oxidizing hydroxyl radical ( rad OH) and reducing aqueous electron (e -aq), to degrade chemical contaminants are alternatives to traditional water treatment methods, and are alternatives as water reuse becomes more generally implemented. Four major statin pharmaceuticals, fluvastatin, lovastatin, pravastatin and simvastatin, were studied, and the absolute bimolecular reaction rate constants with rad OH determined, (6.96±0.16)×10 9, (2.92±0.06)×10 9, (4.16±0.13)×10 9, and (3.13±0.15)×10 9 M -1 s -1, and for e -aq (2.31±0.06)×10 9, (0.45±0.01)×10 9, (1.26±0.01)×10 9, and (0.69±0.02)×10 9 M -1 s -1, respectively. To provide additional information on the radicals formed upon oxidation, transient spectra were measured and the overall reaction efficiency determined. Radical-based destruction mechanisms for destruction of the statins are proposed based on the LC-MS determination of the stable reaction by-products formed using 137Cs γ-irradiation of statin solutions. Knowing the reaction rates, reaction efficiencies and destruction mechanisms of these compounds is essential for the consideration of the use of advanced oxidation/reduction processes for the destruction of statins in aqueous systems.

  2. Treatment of statin compounds by advanced oxidation processes: Kinetic considerations and destruction mechanisms

    International Nuclear Information System (INIS)

    Razavi, Behnaz; Song Weihua; Santoke, Hanoz; Cooper, William J.

    2011-01-01

    This study examined the use of advanced oxidation/reduction processes (AO/RPs) for the destruction of cholesterol lowering statin pharmaceuticals. AO/RPs which utilize the oxidizing hydroxyl radical ( · OH) and reducing aqueous electron (e - aq ), to degrade chemical contaminants are alternatives to traditional water treatment methods, and are alternatives as water reuse becomes more generally implemented. Four major statin pharmaceuticals, fluvastatin, lovastatin, pravastatin and simvastatin, were studied, and the absolute bimolecular reaction rate constants with · OH determined, (6.96±0.16)x10 9 , (2.92±0.06)x10 9 , (4.16±0.13)x10 9 , and (3.13±0.15)x10 9 M -1 s -1 , and for e - aq (2.31±0.06)x10 9 , (0.45±0.01)x10 9 , (1.26±0.01)x10 9 , and (0.69±0.02)x10 9 M -1 s -1 , respectively. To provide additional information on the radicals formed upon oxidation, transient spectra were measured and the overall reaction efficiency determined. Radical-based destruction mechanisms for destruction of the statins are proposed based on the LC-MS determination of the stable reaction by-products formed using 137 Cs γ-irradiation of statin solutions. Knowing the reaction rates, reaction efficiencies and destruction mechanisms of these compounds is essential for the consideration of the use of advanced oxidation/reduction processes for the destruction of statins in aqueous systems.

  3. Treatment of statin compounds by advanced oxidation processes: Kinetic considerations and destruction mechanisms

    Energy Technology Data Exchange (ETDEWEB)

    Razavi, Behnaz, E-mail: brazavi@uci.ed [Urban Water Research Center, Department of Civil and Environmental Engineering, University of California, Irvine, Irvine, CA 92697-2175 (United States); Song Weihua, E-mail: wsong@uci.ed [Urban Water Research Center, Department of Civil and Environmental Engineering, University of California, Irvine, Irvine, CA 92697-2175 (United States); Santoke, Hanoz, E-mail: hsantoke@uci.ed [Urban Water Research Center, Department of Civil and Environmental Engineering, University of California, Irvine, Irvine, CA 92697-2175 (United States); Cooper, William J., E-mail: wcooper@uci.ed [Urban Water Research Center, Department of Civil and Environmental Engineering, University of California, Irvine, Irvine, CA 92697-2175 (United States)

    2011-03-15

    This study examined the use of advanced oxidation/reduction processes (AO/RPs) for the destruction of cholesterol lowering statin pharmaceuticals. AO/RPs which utilize the oxidizing hydroxyl radical ({sup {center_dot}O}H) and reducing aqueous electron (e{sup -}{sub aq}), to degrade chemical contaminants are alternatives to traditional water treatment methods, and are alternatives as water reuse becomes more generally implemented. Four major statin pharmaceuticals, fluvastatin, lovastatin, pravastatin and simvastatin, were studied, and the absolute bimolecular reaction rate constants with {sup {center_dot}O}H determined, (6.96{+-}0.16)x10{sup 9}, (2.92{+-}0.06)x10{sup 9}, (4.16{+-}0.13)x10{sup 9}, and (3.13{+-}0.15)x10{sup 9} M{sup -1} s{sup -1}, and for e{sup -}{sub aq} (2.31{+-}0.06)x10{sup 9}, (0.45{+-}0.01)x10{sup 9}, (1.26{+-}0.01)x10{sup 9}, and (0.69{+-}0.02)x10{sup 9} M{sup -1} s{sup -1}, respectively. To provide additional information on the radicals formed upon oxidation, transient spectra were measured and the overall reaction efficiency determined. Radical-based destruction mechanisms for destruction of the statins are proposed based on the LC-MS determination of the stable reaction by-products formed using {sup 137}Cs {gamma}-irradiation of statin solutions. Knowing the reaction rates, reaction efficiencies and destruction mechanisms of these compounds is essential for the consideration of the use of advanced oxidation/reduction processes for the destruction of statins in aqueous systems.

  4. Investigation of the relevant kinetic processes in the initial stage of a double-arcing instability in oxygen plasmas

    Science.gov (United States)

    Mancinelli, B.; Prevosto, L.; Chamorro, J. C.; Minotti, F. O.; Kelly, H.

    2018-05-01

    A numerical investigation of the kinetic processes in the initial (nanosecond range) stage of the double-arcing instability was developed. The plasma-sheath boundary region of an oxygen-operated cutting torch was considered. The energy balance and chemistry processes in the discharge were described. It is shown that the double-arcing instability is a sudden transition from a diffuse (glow-like) discharge to a constricted (arc-like) discharge in the plasma-sheath boundary region arising from a field-emission instability. A critical electric field value of ˜107 V/m was found at the cathodic part of the nozzle wall under the conditions considered. The field-emission instability drives in turn a fast electronic-to-translational energy relaxation mechanism, giving rise to a very fast gas heating rate of at least ˜109 K/s, mainly due to reactions of preliminary dissociation of oxygen molecules via the highly excited electronic state O2(B3Σu-) populated by electron impact. It is expected that this fast oxygen heating rate further stimulates the discharge contraction through the thermal instability mechanism.

  5. Kinetics and mechanism of thermal processes of nonreversible decomposition of the system N2O4-NO

    International Nuclear Information System (INIS)

    Nesterenko, V.B.; Nichipor, G.V.

    1989-01-01

    Consideration is given to kinetics and mechanism of decomposition of nitrogen oxide in gaseous phase at devated pressures and temperature, decomposition of N 2 O 4 -NO system under flow conditions, as well as to kinetics and mechanism of formation of nitrons oxide. 37 refs.; 13 figs.; 13 tabs

  6. Toluene destruction in the Claus process by sulfur dioxide: A reaction kinetics study

    KAUST Repository

    Sinha, Sourab; Raj, Abhijeet Dhayal; Alshoaibi, Ahmed S.; Alhassan, Saeed M.; Chung, Suk-Ho

    2014-01-01

    The presence of aromatics such as benzene, toluene, and xylene (BTX) as contaminants in the H2S gas stream entering Claus sulfur recovery units has a detrimental effect on catalytic reactors, where BTX forms soot particles and clogs and deactivates the catalysts. BTX oxidation, before they enter catalyst beds, can solve this problem. A theoretical investigation is presented on toluene oxidation by SO2. Density functional theory is used to study toluene radical (benzyl, o-methylphenyl, m-methylphenyl, and p-methylphenyl)-SO2 interactions. The mechanism begins with SO2 addition on the radical through one of the O atoms rather than the S atom. This exothermic reaction involves energy barriers of 4.8-6.1 kJ/mol for different toluene radicals. Thereafter, O-S bond scission takes place to release SO. The reaction rate constants are evaluated to facilitate process simulations. Among four toluene radicals, the resonantly stabilized benzyl radical exhibited lowest SO2 addition rate. A remarkable similarity between toluene oxidation by O2 and by SO2 is observed.

  7. Toluene destruction in the Claus process by sulfur dioxide: A reaction kinetics study

    KAUST Repository

    Sinha, Sourab

    2014-10-22

    The presence of aromatics such as benzene, toluene, and xylene (BTX) as contaminants in the H2S gas stream entering Claus sulfur recovery units has a detrimental effect on catalytic reactors, where BTX forms soot particles and clogs and deactivates the catalysts. BTX oxidation, before they enter catalyst beds, can solve this problem. A theoretical investigation is presented on toluene oxidation by SO2. Density functional theory is used to study toluene radical (benzyl, o-methylphenyl, m-methylphenyl, and p-methylphenyl)-SO2 interactions. The mechanism begins with SO2 addition on the radical through one of the O atoms rather than the S atom. This exothermic reaction involves energy barriers of 4.8-6.1 kJ/mol for different toluene radicals. Thereafter, O-S bond scission takes place to release SO. The reaction rate constants are evaluated to facilitate process simulations. Among four toluene radicals, the resonantly stabilized benzyl radical exhibited lowest SO2 addition rate. A remarkable similarity between toluene oxidation by O2 and by SO2 is observed.

  8. Kinetics and Mechanism of Metal Retention/Release in Geochemical Processes in Soil - Final Report

    Energy Technology Data Exchange (ETDEWEB)

    Taylor, Robert W.

    2000-12-29

    Effective, remediation of soils contaminated with heavy metals requires a better understanding of the mechanisms by which the metals are retained/released in soils over a long period of time. Studies on reaction of Cr(VI) with iron-rich clays indicated that structural iron (II) in these surfaces is capable of reducing chromate to chromium (III). We found that iron (II) either found naturally or produced by treatment of clay with sodium dithionite, effectively reduced Cr (VI) to Cr (III). Thus, in situ remediation of chromium combines reduction of Cr (VI) to Cr (III) and immobilization of chromium on mineral surfaces. During this study, lead sorption on a kaolin surface was found to be a rapid and a pH dependant process in which lead sorption significantly increased with the amount of phosphate on the clay surface. This study verifies that methylmercury cation remains intact when it binds to humic acids, forming a monodentate complex with some sub-population of humic thiol ligands .

  9. Benzene destruction in claus process by sulfur dioxide: A reaction kinetics study

    KAUST Repository

    Sinha, Sourab

    2014-07-02

    Benzene, toluene and xylene (BTX) are present as contaminants in the H 2S gas stream entering a Claus furnace. The exhaust gases from the furnace enter catalytic units, where BTX form soot particles. These particles clog and deactivate the catalysts. A solution to this problem is BTX oxidation before the gases enter catalyst beds. This work presents a theoretical investigation on benzene oxidation by SO2. Density functional theory is used to develop a detailed mechanism for phenyl radical -SO2 interactions. The mechanism begins with SO2 addition to phenyl radical after overcoming an energy barrier of 6.4 kJ/mol. This addition reaction is highly exothermic, where a reaction energy of 182 kJ/mol is released. The most favorable pathway involves O-S bond breakage, leading to the release of SO. A remarkable similarity between the pathways for phenyl radical oxidation by O2 and its oxidation by SO2 is observed. The reaction rate constants are also evaluated to facilitate process simulations. © 2014 American Chemical Society.

  10. From biomass to fuels: hydrotreating of oxygen-containing feeds on a CoMo/Al{sub 2}O{sub 3} hydrodesulfurization catalyst

    Energy Technology Data Exchange (ETDEWEB)

    Viljava, T.-R.

    2001-07-01

    Biomass is a renewable alternative to fossil raw materials in the production of liquid fuels and chemicals. Liquefied biomass contains an abundance of oxygen-containing molecules that need to be removed to improve the stability of the liquids. A hydrotreating process, hydrodeoxygenation (HDO), is used for the purpose. Hydrodeoxygenation is similar to the hydrodesulfurization (HDS) process used in oil refining, relying upon a presulfided CoMo/{gamma}-Al{sub 2}O{sub 2}; catalyst. The stability of the sulfided catalyst is critical in HDO because biocrudes usually do not contain the sulfur compounds needed to maintain the sulfidation of the catalyst. The aim of this work was to examine the role of sulfur in maintaining the activity of the HDO catalyst. Sulfur was introduced as an organic sulfur-containing co-reactant or as a sulfur substituent in an oxygen-containing reactant molecule as a way of simulating mixed feeds composed of biocrudes and conventional crudes, or it was introduced as a low molecular weight sulfiding agent. In addition, the stability of the sulfided catalyst against changes in the feed composition was studied to find out whether the activity of the catalyst could be maintained by carrying out HDO alternately with HDS. Simultaneous HDO and HDS was studied in a batch reactor with model compounds having a sulfur-containing (inercapto or inethylmercapto) and an oxygen-containing (hydroxyl or inethoxy) substituent in the same molecule, and with binary mixtures of mono-substituted benzene compounds. In both cases, the reactions of the oxygencontaining substituents were strongly suppressed as long as a sulfur-containing functionality was present. HDS reactions of inercapto and inethylinercapto groups were either enhanced or retarded in the presence of oxygen-containing functionality. HDS was enhanced when the oxygen-containing substituent was located in Para-position to the sulfur substituent thereby increasing the electronegativity of the sulfur atom and

  11. Dissipation kinetics and effect of processing on imidacloprid and its metabolites in cardamom (Elettaria cardamomum Maton).

    Science.gov (United States)

    Pratheeshkumar, N; Chandran, M; Beevi, S Naseema; Mathew, Thomas Biju; George, Thomas; Paul, Ambily; Xavier, George; Ravi, K Prathibha; Kumar, S Visal; Rajith, R

    2016-01-01

    Dissipation behaviour of the chloronicotinyl insecticide, imidacloprid (Tatamida 17.8 % SL), in fresh and cured cardamom capsules was studied following application at doses 20 and 40 g a.i. ha(-1) in a cardamom plantation of Indian Cardamom Hills (ICH), Idukki, Kerala, India. A single-laboratory ultra performance liquid chromatography mass spectrometry (UPLC-MS/MS) method was developed and validated for the estimation of imidacloprid and its six metabolites (5-hydroxy, olefin, guanidine, urea, 6-chloronicotinic acid and nitrosimine) in fresh and cured cardamom. At the lower dose, the initial deposits of total imidacloprid residues were 1.91 and 7.23 μg g(-1), respectively, in fresh and cured cardamom. At the higher dose, the initial residues were 3.94 and 14.72 μg g(-1), respectively, in fresh and cured capsules. The residues dissipated below the quantitation level of 0.01 μg g(-1) after 21 and 28 days at lower dose and after 28 days for both at higher dose. The half-lives of imidacloprid in fresh and cured cardamom were 4.02 and 3.63 days, respectively, at lower dose and 3.61 days for both at higher dose. The waiting periods of imidacloprid on fresh and cured cardamom at lower and higher doses were 21.40, 27.10, 23.85 and 30.70 days, respectively. The mean processing factor of imidacloprid was 3.96 at 20 g a.i. ha(-1). Amongst metabolites of imidacloprid, urea had maximum residues in fresh and cured cardamom followed by 5-hydroxy and guanidine. Other metabolites such as 6-chloronicotinic acid, olefin and nitrosimine were not detected either in fresh or cured cardamom.

  12. Influence of processes of structure formation in mixed solvent and anion nature on cadmium ions discharge kinetics from water-dimethylformamide electrolyte

    International Nuclear Information System (INIS)

    Kuznetsov, V.V.; Bozhenko, L.G.; Kucherenko, S.S.; Fedorova, O.V.

    1986-01-01

    Electrochemical reaction of cadmium ion discharge in water-dimethylformamide (DMF) solutions is studied. The influence of DMF concentration in the presence of different anions (ClO 4 - , F - , I - ) on both reaction kinetics and mechanism is discussed on the basis of structural transformations in the mixed solvent and near the surface electrode processes

  13. Kinetics of the melting front movement in process of centrifugal induction surfacing of powder material with nanoscale modificaters

    Science.gov (United States)

    Sasnouski, I.; Kurylionak, A.

    2018-03-01

    For solving the problem of improving the powder coatings modified by nanostructure components obtained by induction surfacing method tribological characteristics it is necessary to study the kinetics of the powdered layer melting and define the minimum time of melting. For powdered layer predetermined temperature maintenance at sintering mode stage it is required to determine the temperature difference through blank thickness of the for one hundred-day of the define the warm-up swing on of the stocking up by solving the thermal conductivity stationary problem for quill (hollow) cylinder with internal heat source. Herewith, since in practice thickness of the cylinder wall is much less then its diameter and the temperature difference is comparatively small, the thermal conductivity dependence upon the temperature can be treated as negligible. As it was shown by our previous studies, in the induction heating process under powdered material centrifugal surfacing (i.e. before achieving the melting temperature) the temperature distribution in powdered layer thickness may be considered even. Hereinafter, considering the blank part induction heating process quasi-stationarity under Fo big values, it is possible to consider its internal surface heating as developing with constant velocity. As a result of development the melting front movement mathematical model in a powdered material with nanostructure modifiers the minimum surfacing time is defined. It allows to minimize negative impact of thermal influence on formation of applied coating structure, to raise productivity of the process, to lower power inputs and to ensure saving of nonferrous and high alloys by reducing the allowance for machining. The difference of developed mathematical model of melting front movement from previously known is that the surface temperature from which the heat transfer occures is a variable and varies with a time after the linear law.

  14. Effects of grain source, grain processing, and protein degradability on rumen kinetics and microbial protein synthesis in Boer kids.

    Science.gov (United States)

    Brassard, M-E; Chouinard, P Y; Berthiaume, R; Tremblay, G F; Gervais, R; Martineau, R; Cinq-Mars, D

    2015-11-01

    Microbial protein synthesis in the rumen would be optimized when dietary carbohydrates and proteins have synchronized rates and extent of degradation. The aim of this study was to evaluate the effect of varying ruminal degradation rate of energy and nitrogen sources on intake, nitrogen balance, microbial protein yield, and kinetics of nutrients in the rumen of growing kids. Eight Boer goats (38.2 ± 3.0 kg) were used. The treatments were arranged in a split-plot Latin square design with grain sources (barley or corn) forming the main plots (squares). Grain processing methods and levels of protein degradability formed the subplots in a 2 × 2 factorial arrangement for a total of 8 dietary treatments. The grain processing method was rolling for barley and cracking for corn. Levels of protein degradability were obtained by feeding untreated soybean meal (SBM) or heat-treated soybean meal (HSBM). Each experimental period lasted 21 d, consisting of a 10-d adaptation period, a 7-d digestibility determination period, and a 4-d rumen evacuation and sampling period. Kids fed with corn had higher purine derivatives (PD) excretion when coupled with SBM compared with HSBM and the opposite occurred with barley-fed kids ( ≤ 0.01). Unprocessed grain offered with SBM led to higher PD excretion than with HSBM whereas protein degradability had no effect when processed grain was fed ( ≤ 0.03). Results of the current experiment with high-concentrate diets showed that microbial N synthesis could be maximized in goat kids by combining slowly fermented grains (corn or unprocessed grains) with a highly degradable protein supplement (SBM). With barley, a more rapidly fermented grain, a greater microbial N synthesis was observed when supplementing a low-degradable protein (HSBM).

  15. Stochastic kinetics

    International Nuclear Information System (INIS)

    Colombino, A.; Mosiello, R.; Norelli, F.; Jorio, V.M.; Pacilio, N.

    1975-01-01

    A nuclear system kinetics is formulated according to a stochastic approach. The detailed probability balance equations are written for the probability of finding the mixed population of neutrons and detected neutrons, i.e. detectrons, at a given level for a given instant of time. Equations are integrated in search of a probability profile: a series of cases is analyzed through a progressive criterium. It tends to take into account an increasing number of physical processes within the chosen model. The most important contribution is that solutions interpret analytically experimental conditions of equilibrium (moise analysis) and non equilibrium (pulsed neutron measurements, source drop technique, start up procedures)

  16. Glyoxal processing by aerosol multiphase chemistry: towards a kinetic modeling framework of secondary organic aerosol formation in aqueous particles

    Directory of Open Access Journals (Sweden)

    B. Ervens

    2010-09-01

    Full Text Available This study presents a modeling framework based on laboratory data to describe the kinetics of glyoxal reactions that form secondary organic aerosol (SOA in aqueous aerosol particles. Recent laboratory results on glyoxal reactions are reviewed and a consistent set of empirical reaction rate constants is derived that captures the kinetics of glyoxal hydration and subsequent reversible and irreversible reactions in aqueous inorganic and water-soluble organic aerosol seeds. Products of these processes include (a oligomers, (b nitrogen-containing products, (c photochemical oxidation products with high molecular weight. These additional aqueous phase processes enhance the SOA formation rate in particles and yield two to three orders of magnitude more SOA than predicted based on reaction schemes for dilute aqueous phase (cloud chemistry for the same conditions (liquid water content, particle size.

    The application of the new module including detailed chemical processes in a box model demonstrates that both the time scale to reach aqueous phase equilibria and the choice of rate constants of irreversible reactions have a pronounced effect on the predicted atmospheric relevance of SOA formation from glyoxal. During day time, a photochemical (most likely radical-initiated process is the major SOA formation pathway forming ∼5 μg m−3 SOA over 12 h (assuming a constant glyoxal mixing ratio of 300 ppt. During night time, reactions of nitrogen-containing compounds (ammonium, amines, amino acids contribute most to the predicted SOA mass; however, the absolute predicted SOA masses are reduced by an order of magnitude as compared to day time production. The contribution of the ammonium reaction significantly increases in moderately acidic or neutral particles (5 < pH < 7.

    Glyoxal uptake into ammonium sulfate seed under dark conditions can be represented with a single reaction parameter keffupt that does not depend

  17. Acceleration and sensitivity analysis of lattice kinetic Monte Carlo simulations using parallel processing and rate constant rescaling.

    Science.gov (United States)

    Núñez, M; Robie, T; Vlachos, D G

    2017-10-28

    Kinetic Monte Carlo (KMC) simulation provides insights into catalytic reactions unobtainable with either experiments or mean-field microkinetic models. Sensitivity analysis of KMC models assesses the robustness of the predictions to parametric perturbations and identifies rate determining steps in a chemical reaction network. Stiffness in the chemical reaction network, a ubiquitous feature, demands lengthy run times for KMC models and renders efficient sensitivity analysis based on the likelihood ratio method unusable. We address the challenge of efficiently conducting KMC simulations and performing accurate sensitivity analysis in systems with unknown time scales by employing two acceleration techniques: rate constant rescaling and parallel processing. We develop statistical criteria that ensure sufficient sampling of non-equilibrium steady state conditions. Our approach provides the twofold benefit of accelerating the simulation itself and enabling likelihood ratio sensitivity analysis, which provides further speedup relative to finite difference sensitivity analysis. As a result, the likelihood ratio method can be applied to real chemistry. We apply our methodology to the water-gas shift reaction on Pt(111).

  18. Removal of cationic pollutants from water by xanthated corn cob: optimization, kinetics, thermodynamics, and prediction of purification process.

    Science.gov (United States)

    Kostić, Miloš; Đorđević, Miloš; Mitrović, Jelena; Velinov, Nena; Bojić, Danijela; Antonijević, Milan; Bojić, Aleksandar

    2017-07-01

    The removal of Cr(III) ions and methylene blue (MB) from aqueous solutions by xanthated corn cob (xCC) in batch conditions was investigated. The sorption capacity of xCC strongly depended of the pH, and increase when the pH rises. The kinetics was well fitted by pseudo-second-order and Chrastil's model. Sorption of Cr(III) ions and MB on xCC was rapid during the first 20 min of contact time and, thereafter, the biosorption rate decrease gradually until reaching equilibrium. The maximum sorption capacity of 17.13 and 83.89 mg g -1 for Cr(III) ions and MB, respectively, was obtained at 40 °C, pH 5, and sorbent dose 4 g dm -3 for removal of Cr(III) ions and 1 g dm -3 for removal of MB. The prediction of purification process was successfully carried out, and the verification of theoretically calculated amounts of sorbent was confirmed by using packed-bed column laboratory system with recirculation of the aqueous phase. The wastewater from chrome plating industry was successfully purified, i.e., after 40 min concentration of Cr(III) ions was decreased lower than 0.1 mg dm -3 . Also, removal of MB from the river water was successfully carried out and after 40 min, removal efficiency was about 94%.

  19. Hydrotreating and hydrocracking of Athabasca bitumen derived heavy gas oils using NiMo catalyst supported on titania modified alumina

    Energy Technology Data Exchange (ETDEWEB)

    Ferdous, D.; Bakhshi, N.N.; Dalai, A.K.; Adjaye, J. [Saskatchewan Univ., Saskatoon, SK (Canada). Dept. of Chemical Engineering, Catalysis and Chemical Reaction Engineering Laboratories]|[Syncrude Canada Ltd., Edmonton, AB (Canada)

    2006-07-01

    Different NiMo catalysts supported on titania modified Al{sub 2}O{sub 3} were synthesized and characterized in an effort to study the hydrodenitrigenation (HDN) and hydrodesulfurization (HDS) of different gas oils derived from Athabasca bitumen. The Al{sub x}O{sub 3} supports were modified by incorporating up to 9 wt per cent titanium (Ti). All modified supports as well as fresh and spent catalysts were characterized by BET surface area, pore volume and pore diameter, XRD, TPR, TPD and SEM. A trickle-bed reactor using 3 different gas oils from the Athabasca bitumen was used to test the initial activity of these catalysts. The 3 oils were light gas oil (LGO), heavy gas oil (HGO) and blended gas oil having 50 per cent LGO and 50 per cent HGO. The study showed that nitrogen conversion increased for all the gas oils when Ti was incorporated into the alumina. With an increase in Ti concentrations from 0 to 6 wt per cent, nitrogen conversion increased from 57-69.5 wt per cent, 75-80.2 wt per cent, 83-91.5 wt per cent and for LGO, HGO and blended, respectively. Nearly 86 wt per cent sulphur conversion was obtained for all Ti concentrations for LGO, while HGO and blended sulphur conversions were in the range of 96-97 wt per cent. Detailed hydrotreating and hydrocracking of HGO was then performed using the 6 wt per cent Ti modified catalyst because it achieved the maximum nitrogen conversion. This paper also presented the temperature, pressure and liquid hourly space velocity for this catalyst along with the maximum nitrogen and sulphur conversions. Results were compared with those of commercial catalysts. tabs., figs.

  20. Biodegradation of phenol with chromium(VI) reduction in an anaerobic fixed-biofilm process-Kinetic model and reactor performance

    International Nuclear Information System (INIS)

    Lin, Yen-Hui; Wu, Chih-Lung; Hsu, Chih-Hao; Li, Hsin-Lung

    2009-01-01

    A mathematical model system was derived to describe the simultaneous removal of phenol biodegradation with chromium(VI) reduction in an anaerobic fixed-biofilm reactor. The model system incorporates diffusive mass transport and double Monod kinetics. The model was solved using a combination of the orthogonal collocation method and Gear's method. A laboratory-scale column reactor was employed to validate the kinetic model system. Batch kinetic tests were conducted independently to evaluate the biokinetic parameters used in the model simulation. The removal efficiencies of phenol and chromium(VI) in an anaerobic fixed-biofilm process were approximately 980 mg/g and 910 mg/g, respectively, under a steady-state condition. In the steady state, model-predicted biofilm thickness reached up to 350 μm and suspended cells in the effluent were 85 mg cell/l. The experimental results agree closely with the results of the model simulations.

  1. Ultrasound-assisted lipase-catalyzed synthesis of D-isoascorbyl palmitate: process optimization and Kinetic evaluation.

    Science.gov (United States)

    Cui, Feng-Jie; Zhao, Hong-Xia; Sun, Wen-Jing; Wei, Zhuan; Yu, Si-Lian; Zhou, Qiang; Dong, Ying

    2013-12-09

    D-isoascorbic acid is a food antioxidant additive and used in accordance with Good Manufacturing Practice (GMP). High solubility in water (about 150 g/L at 25°C) reduces its effectiveness in stabilizing fats and oils. Our research group had successfully synthesized D-isoascorbyl palmitate using immobilized lipase Novozym 435 as a biocatalyst. Low production efficiency of D-isoascorbyl palmitate is still a problem for industrial production due to the long reaction time of over 24 h. In the present work, ultrasonic treatment was applied for accelerating the reaction process. The operation parameters were optimized to obtain the maximum D-isoascorbyl palmitate conversion rate by using a 5-level-4-factor Central Composite Design (CCD) and Response Surface Methdology (RSM). The reaction apparent kinetic parameters under the ultrasound treatment and mechanical shaking conditions were also determined and compared. Results showed that ultrasound treatment decreased the reaction time by over 50%. D-isoascorbyl palmitate yielded to 94.32 ± 0.17% and the productivity reached to 8.67 g L-1 h-1 under the optimized conditions as: 9% of enzyme load (w/w), 61°C of reaction temperature, 1:5 of D- isoascorbic-to-palmitic acid molar ratio, and 137 W of the ultrasound power. The immobilized lipase Novozym 435 could be reused for 7 times with 65% of the remained D-isoascorbyl palmitate conversion rate. The reaction kinetics showed that the maximum apparent reaction rate (vmax) of the ultrasound-assisted reaction was 2.85 times higher than that of the mechanical shaking, which proved that ultrasound treatment significantly enhanced the reaction efficiency. A systematic study on ultrasound-assisted enzymatic esterification for D-isoascorbyl palmitate production is reported. The results show a promising perspective of the ultrasound technique to reduce the reaction time and improve the production efficiency. The commercial D-isoascorbyl palmitate synthesis will be potentially

  2. Model and system learners, optimal process constructors and kinetic theory-based goal-oriented design: A new paradigm in materials and processes informatics

    Science.gov (United States)

    Abisset-Chavanne, Emmanuelle; Duval, Jean Louis; Cueto, Elias; Chinesta, Francisco

    2018-05-01

    Traditionally, Simulation-Based Engineering Sciences (SBES) has relied on the use of static data inputs (model parameters, initial or boundary conditions, … obtained from adequate experiments) to perform simulations. A new paradigm in the field of Applied Sciences and Engineering has emerged in the last decade. Dynamic Data-Driven Application Systems [9, 10, 11, 12, 22] allow the linkage of simulation tools with measurement devices for real-time control of simulations and applications, entailing the ability to dynamically incorporate additional data into an executing application, and in reverse, the ability of an application to dynamically steer the measurement process. It is in that context that traditional "digital-twins" are giving raise to a new generation of goal-oriented data-driven application systems, also known as "hybrid-twins", embracing models based on physics and models exclusively based on data adequately collected and assimilated for filling the gap between usual model predictions and measurements. Within this framework new methodologies based on model learners, machine learning and kinetic goal-oriented design are defining a new paradigm in materials, processes and systems engineering.

  3. Process for recycling mixed-cathode materials from spent lithium-ion batteries and kinetics of leaching.

    Science.gov (United States)

    Li, Li; Bian, Yifan; Zhang, Xiaoxiao; Guan, Yibiao; Fan, Ersha; Wu, Feng; Chen, Renjie

    2018-01-01

    A "grave-to-cradle" process for the recycling of spent mixed-cathode materials (LiCoO 2 , LiCo 1/3 Ni 1/3 Mn 1/3 O 2 , and LiMn 2 O 4 ) has been proposed. The process comprises an acid leaching followed by the resynthesis of a cathode material from the resulting leachate. Spent cathode materials were leached in citric acid (C 6 H 8 O 7 ) and hydrogen peroxide (H 2 O 2 ). Optimal leaching conditions were obtained at a leaching temperature of 90 °C, a H 2 O 2 concentration of 1.5 vol%, a leaching time of 60 min, a pulp density of 20 g L -1 , and a citric acid concentration of 0.5 M. The leaching efficiencies of Li, Co, Ni, and Mn exceeded 95%. The leachate was used to resynthesize new LiCo 1/3 Ni 1/3 Mn 1/3 O 2 material by using a sol-gel method. A comparison of the electrochemical properties of the resynthesized material (NCM-spent) with that synthesized directly from original chemicals (NCM-syn) indicated that the initial discharge capacity of NCM-spent at 0.2 C was 152.8 mA h g -1 , which was higher than the 149.8 mA h g -1 of NCM-syn. After 160 cycles, the discharge capacities of the NCM-spent and NCM-syn were 140.7 mA h g -1 and 121.2 mA h g -1 , respectively. After discharge at 1 C for 300 cycles, the NCM-spent material remained a higher capacity of 113.2 mA h g -1 than the NCM-syn (78.4 mA h g -1 ). The better performance of the NCM-spent resulted from trace Al doping. A new formulation based on the shrinking-core model was proposed to explain the kinetics of the leaching process. The activation energies of the Li, Co, Ni, and Mn leaching were calculated to be 66.86, 86.57, 49.46, and 45.23 kJ mol -1 , respectively, which indicates that the leaching was a chemical reaction-controlled process. Copyright © 2017 Elsevier Ltd. All rights reserved.

  4. An ab initio study of hydrotreating of thiirene and thiirane on MoS 3 ...

    African Journals Online (AJOL)

    The catalytic site used is based on molybdenum disulfide (MoS2), which is considered ... Two steps characterise the desulfurization process: the adsorption and the ... catalytic site and molecules obtained in previous works in the EHT method.

  5. Parametric Investigation of the Isothermal Kinetics of Growth of Graphene on a Nickel Catalyst in the Process of Chemical Vapor Deposition of Hydrocarbons

    Science.gov (United States)

    Futko, S. I.; Shulitskii, B. G.; Labunov, V. A.; Ermolaeva, E. M.

    2016-11-01

    A kinetic model of isothermal synthesis of multilayer graphene on the surface of a nickel foil in the process of chemical vapor deposition, on it, of hydrocarbons supplied in the pulsed regime is considered. The dependences of the number of graphene layers formed and the time of their growth on the temperature of the process, the concentration of acetylene, and the thickness of the nickel foil were calculated. The regime parameters of the process of chemical vapor deposition, at which single-layer graphene and bi-layer graphene are formed, were determined. The dynamics of growth of graphene domains at chemical-vapor-deposition parameters changing in wide ranges was investigated. It is shown that the time dependences of the rates of growth of single-layer graphene and bi-layer graphene are nonlinear in character and that they are determined by the kinetics of nucleation and growth of graphene and the diffusion flow of carbon atoms in the nickel foil.

  6. Kinetics and mechanisms of metal retention/release in geochemical processes in soil. 1998 annual progress report

    International Nuclear Information System (INIS)

    Taylor, R.W.

    1998-01-01

    'The long-term fate of toxic metals in soils cannot be precisely predicted, and often remediation recommendations and techniques may be ineffective or unnecessary. This work will generate basic knowledge on the kinetics and mechanism(s) of heavy metal retention/release by soil mineral colloids. The information should assist in improving remediation strategies for toxic heavy metal contaminated soils. The objectives are: (1) To determine the effects of residence time on the mechanisms of Cr(VI), Cu(II), Co(II), Cd(II), Pb(II), and Ni(II) sorption/release on Fe and Al oxide and clay mineral surfaces using kinetic studies coupled to extended x-ray absorption fine structure (EXAFS) spectroscopy and fourier transform infrared (FTIR) spectroscopy. (2) To study the effect of temperature, pH, and phosphate on metal sorption by oxides, and derive thermodynamic parameters to describe the sorption process. As of June, 16, 1997 several clay minerals were tested for their efficiency of removing Cr from aqueous systems. The materials tested--smectite, vermiculites, illites, and kaolinite--represent the natural clay minerals that are abundant in soils and sediments. The clays were used in either their original or reduced (reduced with sodium dithionite) forms. The experimental result indicate that the reduced clays acted as an efficient remover of Cr(VI) from an aqueous system. The XANES spectra of Cr-treated clays provided evidence that the clays reduced Cr(VI) to Cr(III) and immobilized Cr in the clays at the same time. Sodium dithionite applied directly into aqueous systems reduced Cr(VI) to Cr(III), but could not immobilize Cr even in the presence of the clays. The Cr(VI) removal capacity varied with the clay mineral type and the structural Fe content. For the clays used in this study, the removal capacity follows the orders of smectites > vermiculites and illites > kaolinite. Within the same type of clay minerals, reduction of Cr(VI) is highly related to the ferrous iron

  7. Kinetic Analysis of Dynamic Positron Emission Tomography Data using Open-Source Image Processing and Statistical Inference Tools.

    Science.gov (United States)

    Hawe, David; Hernández Fernández, Francisco R; O'Suilleabháin, Liam; Huang, Jian; Wolsztynski, Eric; O'Sullivan, Finbarr

    2012-05-01

    In dynamic mode, positron emission tomography (PET) can be used to track the evolution of injected radio-labelled molecules in living tissue. This is a powerful diagnostic imaging technique that provides a unique opportunity to probe the status of healthy and pathological tissue by examining how it processes substrates. The spatial aspect of PET is well established in the computational statistics literature. This article focuses on its temporal aspect. The interpretation of PET time-course data is complicated because the measured signal is a combination of vascular delivery and tissue retention effects. If the arterial time-course is known, the tissue time-course can typically be expressed in terms of a linear convolution between the arterial time-course and the tissue residue. In statistical terms, the residue function is essentially a survival function - a familiar life-time data construct. Kinetic analysis of PET data is concerned with estimation of the residue and associated functionals such as flow, flux, volume of distribution and transit time summaries. This review emphasises a nonparametric approach to the estimation of the residue based on a piecewise linear form. Rapid implementation of this by quadratic programming is described. The approach provides a reference for statistical assessment of widely used one- and two-compartmental model forms. We illustrate the method with data from two of the most well-established PET radiotracers, (15)O-H(2)O and (18)F-fluorodeoxyglucose, used for assessment of blood perfusion and glucose metabolism respectively. The presentation illustrates the use of two open-source tools, AMIDE and R, for PET scan manipulation and model inference.

  8. Kinetic Typography

    DEFF Research Database (Denmark)

    van Leeuwen, Theo; Djonov, Emilia

    2014-01-01

    After discussing broad cultural drivers behind the development of kinetic typography, the chapter outlines an approach to analysing kinetic typography which is based on Halliday's theory of transitivity, as applied by Kress and Van Leeuwen to visual images.......After discussing broad cultural drivers behind the development of kinetic typography, the chapter outlines an approach to analysing kinetic typography which is based on Halliday's theory of transitivity, as applied by Kress and Van Leeuwen to visual images....

  9. Investigation of Spark Ignition and Autoignition in Methane and Air Using Computational Fluid Dynamics and Chemical Reaction Kinetics. A numerical Study of Ignition Processes in Internal Combustion Engines

    Energy Technology Data Exchange (ETDEWEB)

    Nordrik, R.

    1993-12-01

    The processes in the combustion chamber of internal combustion engines have received increased attention in recent years because their efficiencies are important both economically and environmentally. This doctoral thesis studies the ignition phenomena by means of numerical simulation methods. The fundamental physical relations include flow field conservation equations, thermodynamics, chemical reaction kinetics, transport properties and spark modelling. Special attention is given to the inclusion of chemical kinetics in the flow field equations. Using his No Transport of Radicals Concept method, the author reduces the computational efforts by neglecting the transport of selected intermediate species. The method is validated by comparison with flame propagation data. A computational method is described and used to simulate spark ignition in laminar premixed methane-air mixtures and the autoignition process of a methane bubble surrounded by hot air. The spark ignition simulation agrees well with experimental results from the literature. The autoignition simulation identifies the importance of diffusive and chemical processes acting together. The ignition delay times exceed the experimental values found in the literature for premixed ignition delay, presumably because of the mixing process and lack of information on low temperature reactions in the skeletal kinetic mechanism. Transient turbulent methane jet autoignition is simulated by means of the KIVA-II code. Turbulent combustion is modelled by the Eddy Dissipation Concept. 90 refs., 81 figs., 3 tabs.

  10. A kinetic Monte Carlo simulation method of van der Waals epitaxy for atomistic nucleation-growth processes of transition metal dichalcogenides.

    Science.gov (United States)

    Nie, Yifan; Liang, Chaoping; Cha, Pil-Ryung; Colombo, Luigi; Wallace, Robert M; Cho, Kyeongjae

    2017-06-07

    Controlled growth of crystalline solids is critical for device applications, and atomistic modeling methods have been developed for bulk crystalline solids. Kinetic Monte Carlo (KMC) simulation method provides detailed atomic scale processes during a solid growth over realistic time scales, but its application to the growth modeling of van der Waals (vdW) heterostructures has not yet been developed. Specifically, the growth of single-layered transition metal dichalcogenides (TMDs) is currently facing tremendous challenges, and a detailed understanding based on KMC simulations would provide critical guidance to enable controlled growth of vdW heterostructures. In this work, a KMC simulation method is developed for the growth modeling on the vdW epitaxy of TMDs. The KMC method has introduced full material parameters for TMDs in bottom-up synthesis: metal and chalcogen adsorption/desorption/diffusion on substrate and grown TMD surface, TMD stacking sequence, chalcogen/metal ratio, flake edge diffusion and vacancy diffusion. The KMC processes result in multiple kinetic behaviors associated with various growth behaviors observed in experiments. Different phenomena observed during vdW epitaxy process are analysed in terms of complex competitions among multiple kinetic processes. The KMC method is used in the investigation and prediction of growth mechanisms, which provide qualitative suggestions to guide experimental study.

  11. Ozonation of hospital raw wastewaters for cytostatic compounds removal. Kinetic modelling and economic assessment of the process

    Energy Technology Data Exchange (ETDEWEB)

    Ferre-Aracil, J. [Universitat Politècnica de València – EPSA, Department of Chemical and Nuclear Engineering. Institute for Industrial, Radiophysical and Environmental Safety (ISIRYM), Pl. Ferrandiz i Carbonell, 03801 Alcoi, Alicante (Spain); Valcárcel, Y. [Environmental Health and Ecotoxicology Research Group, Universidad Rey Juan Carlos, Avd. Atenas s/n, Móstoles, 28922 Alcorcón (Spain); Negreira, N.; López de Alda, M. [Water and Soil Quality Research Group, Department of Environmental Chemistry, Institute of Environmental Assessment and Water Research (IDAEA-CSIC), C/ Jordi Girona 18-26, 08034 Barcelona (Spain); Barceló, D. [Water and Soil Quality Research Group, Department of Environmental Chemistry, Institute of Environmental Assessment and Water Research (IDAEA-CSIC), C/ Jordi Girona 18-26, 08034 Barcelona (Spain); Catalan Institute for Water Research (ICRA), H2O Building, Scientific and Technological Park of the University of Girona, Emili Grahit 101, 17003 Girona (Spain); Cardona, S.C. [Universitat Politècnica de València – EPSA, Department of Chemical and Nuclear Engineering. Institute for Industrial, Radiophysical and Environmental Safety (ISIRYM), Pl. Ferrandiz i Carbonell, 03801 Alcoi, Alicante (Spain); Navarro-Laboulais, J., E-mail: jnavarla@iqn.upv.es [Universitat Politècnica de València – EPSA, Department of Chemical and Nuclear Engineering. Institute for Industrial, Radiophysical and Environmental Safety (ISIRYM), Pl. Ferrandiz i Carbonell, 03801 Alcoi, Alicante (Spain)

    2016-06-15

    The kinetics of the ozone consumption for the pretreatment of hospital wastewater has been analysed in order to determine the reaction rate coefficients between the ozone and the readily oxidisabled organic matter and cytostatic compounds. The wastewater from a medium size hospital was treated with ozone and peroxone methodologies, varying the ozone concentration, the reaction time and the hydrogen peroxide doses. The analysis shows that there are four cytostatic compounds, i.e. irinotecan, ifosfamide, cyclophosphamide and capecitabine, detected in the wastewaters and they are completely removed with reasonably short times after the ozone treatment. Considering the reactor geometry, the gas hydrodynamics, the mass transfer of ozone from gas to liquid and the reaction of all oxidisable compounds of the wastewater it is possible to determine the chemical ozone demand, COzD, of the sample as 256 mg O{sub 3} L{sup −1} and the kinetic rate coefficient with the dissolved organic matter as 8.4 M{sup −1} s{sup −1}. The kinetic rate coefficient between the ozone and the cyclophosphamide is in the order of 34.7 M{sup −1} s{sup −1} and higher for the other cytostatics. The direct economic cost of the treatment was evaluated considering this reaction kinetics and it is below 0.3 €/m{sup 3} under given circumstances. - Highlights: • 17 cytostatic compounds were analysed and 4 detected by SPE-LC/MS-MS. • The ozonation is 100% effective on the removal of the detected cytostatics. • The kinetics of cytostatic ozonation reaction is modeled by competitive kinetics. • The economic cost of the treatment of hospital wastewater was assessed.

  12. Ozonation of hospital raw wastewaters for cytostatic compounds removal. Kinetic modelling and economic assessment of the process

    International Nuclear Information System (INIS)

    Ferre-Aracil, J.; Valcárcel, Y.; Negreira, N.; López de Alda, M.; Barceló, D.; Cardona, S.C.; Navarro-Laboulais, J.

    2016-01-01

    The kinetics of the ozone consumption for the pretreatment of hospital wastewater has been analysed in order to determine the reaction rate coefficients between the ozone and the readily oxidisabled organic matter and cytostatic compounds. The wastewater from a medium size hospital was treated with ozone and peroxone methodologies, varying the ozone concentration, the reaction time and the hydrogen peroxide doses. The analysis shows that there are four cytostatic compounds, i.e. irinotecan, ifosfamide, cyclophosphamide and capecitabine, detected in the wastewaters and they are completely removed with reasonably short times after the ozone treatment. Considering the reactor geometry, the gas hydrodynamics, the mass transfer of ozone from gas to liquid and the reaction of all oxidisable compounds of the wastewater it is possible to determine the chemical ozone demand, COzD, of the sample as 256 mg O 3 L −1 and the kinetic rate coefficient with the dissolved organic matter as 8.4 M −1 s −1 . The kinetic rate coefficient between the ozone and the cyclophosphamide is in the order of 34.7 M −1 s −1 and higher for the other cytostatics. The direct economic cost of the treatment was evaluated considering this reaction kinetics and it is below 0.3 €/m 3 under given circumstances. - Highlights: • 17 cytostatic compounds were analysed and 4 detected by SPE-LC/MS-MS. • The ozonation is 100% effective on the removal of the detected cytostatics. • The kinetics of cytostatic ozonation reaction is modeled by competitive kinetics. • The economic cost of the treatment of hospital wastewater was assessed.

  13. Volatile fatty acid degradation kinetics in anaerobic process; Cinetica de la degradacion de acidos grasos volatiles en procesos anaerobios

    Energy Technology Data Exchange (ETDEWEB)

    Riscado, S.; Osuna, B.; Iza, J.; Ruiz, E. [Universidad del Pais Vasco. Bilbao (Spain)

    1998-10-01

    While searching for the optimal substrate load for anaerobic toxicity assays, the inhibition caused by the propionic acid has been addressed. Lab scale experiments have been carried out to assess the effects of different loads and acid ratios. Results bad been subjected to kinetic analysis and show the degradation follows a first order kinetic, and acetic is easier to degrade than propionic acid. The optimal load for a 100 ml vial assay is composed of 158 mg COD of the 3:1:1 HAc:HPr:HBu mixture. (Author) 9 refs.

  14. From particle systems to learning processes. Comment on "Collective learning modeling based on the kinetic theory of active particles" by Diletta Burini, Silvana De Lillo, and Livio Gibelli

    Science.gov (United States)

    Lachowicz, Mirosław

    2016-03-01

    The very stimulating paper [6] discusses an approach to perception and learning in a large population of living agents. The approach is based on a generalization of kinetic theory methods in which the interactions between agents are described in terms of game theory. Such an approach was already discussed in Ref. [2-4] (see also references therein) in various contexts. The processes of perception and learning are based on the interactions between agents and therefore the general kinetic theory is a suitable tool for modeling them. However the main question that rises is how the perception and learning processes may be treated in the mathematical modeling. How may we precisely deliver suitable mathematical structures that are able to capture various aspects of perception and learning?

  15. Experimental and theoretical investigations on the carbon dioxide gas hydrate formation kinetics at the onset of turbidity regarding CO2 capture and sequestration processes

    International Nuclear Information System (INIS)

    ZareNezhad, Bahman; Mottahedin, Mona; Varaminian, Farshad

    2013-01-01

    The carbon dioxide gas hydrate formation kinetics at the onset of turbidity is experimentally and theoretically investigated. It is shown that the time-dependent heterogeneous nucleation and growth kinetics are simultaneously governing the hydrate formation process at the onset of turbidity. A new approach is also presented for determination of gas hydrate-liquid interfacial tension. The CO 2 hydrate-liquid interfacial tension according to the suggested heterogeneous nucleation mechanism is found to be about 12.7 mJ/m 2 . The overall average absolute deviation between predicted and measured CO 2 molar consumption is about 0.61%, indicating the excellent accuracy of the proposed model for studying the hydrate-based CO 2 capture and sequestration processes over wide ranges of pressures and temperatures

  16. Cold Incineration of Chlorophenols in Aqueous Solution by Advanced Electrochemical Process Electro-Fenton. Effect of Number and Position of Chlorine Atoms on the Degradation Kinetics

    Science.gov (United States)

    Oturan, Nihal; Panizza, Marco; Oturan, Mehmet A.

    2009-09-01

    This study reports the kinetics of the degradation of several chlorophenols (CPs), such as monochlorophenols (2-chlorophenol and 4-chlorophenol), dichlorophenols (2,4-dichlorophenol and 2,6- dichlorophenol), trichlorophenols (2,3,5- trichlorophenol and 2,4,5-trichlorophenol), 2,3,5,6-tetrachlorophenol, and pentachlorophenol, by the electro-Fenton process using a carbon felt cathode and a Pt anode. The effect of number and the position of the chlorine atoms in the aromatic ring on the oxidative degradation rate was evaluated and discussed. The oxidation reaction of all the CPs with hydroxyl radicals evidenced a pseudo-first-order kinetics and the rate constant decreased with increasing the number of chlorine atoms. The absolute rate constant of second-order reaction kinetics between CPs and •OH was determined by the competition kinetics method in the range of (3.56-7.75) × 109 M-1 s-1 and follows the same sequence of the apparent rate constants. The mineralization of several CPs and of a mixture of all CPs under study was monitored by the total organic carbon (TOC) removal and the chlorine release during mineralization was followed by ion chromatography. Our results demonstrated that more chlorinated phenols are more difficult to mineralize; however for all the tested CPs, almost quantitative release of chloride ions was obtained after 6 h of treatment.

  17. Commercial Approval Plan for Synthetic Jet Fuel from Hydrotreated Fats and Oils

    Science.gov (United States)

    2009-02-18

    driven by their experience, some of it very negative, with the other more well known organic oil derived fuel, BioDiesel. BioDiesel is methyl ester of...the fatty acid ( FAME ) that comes from the triglycerides that compose the organic oil. The HRJ SPKs are deoxygenated materials that are processed in...SwRI Cu PE506 * Semi-Quant Survey ICP/MS * Organic Elements C:H D5291 * N D4629 * S D5453 * Acid Number D3242 * Carbonyls, alcohols, esters , phenols

  18. The importance of pre-treatment of spent hydrotreating catalysts on metals recovery

    Directory of Open Access Journals (Sweden)

    Alexandre Luiz de Souza Pereira

    2011-01-01

    Full Text Available This work describes a three-step pre-treatment route for processing spent commercial NiMo/Al2O3 catalysts. Extraction of soluble coke with n-hexane and/or leaching of foulant elements with oxalic acid were performed before burning insoluble coke under air. Oxidized catalysts were leached with 9 mol L-1 sulfuric acid. Iron was the only foulant element partially leached by oxalic acid. The amount of insoluble matter in sulfuric acid was drastically reduced when iron and/or soluble coke were previously removed. Losses of active phase metals (Ni, Mo during leaching with oxalic acid were compensated by the increase of their recovery in the sulfuric acid leachate.

  19. The importance of pre-treatment of spent hydrotreating catalysts on metals recovery

    Energy Technology Data Exchange (ETDEWEB)

    Pereira, Alexandre Luiz de Souza; Silva, Cristiano Nunes da; Afonso, Julio Carlos, E-mail: julio@iq.ufrj.b [Universidade Federal do Rio de Janeiro (IQ/UFRJ), RJ (Brazil). Inst. de Quimica. Dept. de Quimica Analitica; Mantovano, Jose Luiz [Instituto de Engenharia Nuclear (CNEN/IEN-RJ), Rio de Janeiro, RJ (Brazil). Dept. de Quimica e Materiais Nucleares

    2011-07-01

    This work describes a three-step pre-treatment route for processing spent commercial Ni Mo/Al{sub 2}O{sub 3} catalysts. Extraction of soluble coke with n-hexane and/or leaching of foulant elements with oxalic acid were performed before burning insoluble coke under air. Oxidized catalysts were leached with 9 mol L{sup -1} sulfuric acid. Iron was the only foulant element partially leached by oxalic acid. The amount of insoluble matter in sulfuric acid was drastically reduced when iron and/or soluble coke were previously removed. Losses of active phase metals (Ni, Mo) during leaching with oxalic acid were compensated by the increase of their recovery in the sulfuric acid leachate. (author)

  20. Kinetic research on heterogeneously catalysed processes: a questionnaire on the state-of-the-art in industry

    NARCIS (Netherlands)

    Bos, A.N.R.; Lefferts, Leonardus; Marin, G.B.; Steijns, M.H.G.M.

    1997-01-01

    On the initiative of the Working Party `Chemical Engineering in the Applications of Catalysis¿ of the European Federation of Chemical Engineering an assessment of the issues in the determination and application of kinetic data within the European industry was performed. The basis of the analysis

  1. The kinetics of sterane biological marker release and degradation processes during the hydrous pyrolysis of vitrinite kerogen

    Science.gov (United States)

    Abbott, G. D.; Wang, G. Y.; Eglinton, T. I.; Home, A. K.; Petch, G. S.

    1990-09-01

    The hydrous pyrolysis of a mineral-free vitrinite kerogen (Dinantian coal Lower Carboniferous, North East England) has been carried out at four temperatures (270, 300, 330, and 350°C) for heating times ranging from 2 to 648 h. No significant differences in the epimer-based maturation parameters 20S/(20S + 20R)-5α(H),14α(H),17α(H) C 29 non-rearranged steranes and 22S/(22S+22R)-17α(H), 21β(H) homohopanes were found for a comparison between "expelled oil" and "bitumen" fractions in the resulting pyrolysates. A deuterated model compound ((20R)-5α(H),14α(H),17α(H)-[2,2,4,4-d 4] cholestane) was added to a number of preextracted kerogens (vitrinite, Kimmeridge, Messel and Monterey) and the mixtures were heated under typical hydrous pyrolysis conditions. These experiments showed that direct chiral isomerisation at C-20 in the non-rearranged steranes appears to be relatively unimportant during hydrous pyrolysis which has also been suggested by other recent studies on geological samples.A kinetic model comprising consecutive release and degradation processes was derived to measure first-order rate coefficients from the bi-exponential concentration-time functions of both the (20R)-and (20S)-5α(H),14α(H),17α(H) C 29 "free" steranes in the vitrinite kerogen pyrolysates. This data was then used to calculate preliminary Arrhenius parameters for release ((20S): ΔEa = 125 ± 30 kJ mol -1, A ≈ 4.7 × 10 5 s -1;(20R): ΔEa = 151 ± 39 kJ mol -1, A ≈ 2.7 × 10 9 s -1) and degradation ((20S): ΔEa = 104 ± 22 kJ mol -1, A ≈ 5.8 × 10 3 s -1; (20R): Δa = 87 ± 6 kJ mol -1, A ≈ 2.2 × 10 2 s -1) of the above individual isomers and the values were found to be consistent with a free-radical chain mechanism. This work helps in the greater understanding of the important biomarker reactions that prevail in hydrous pyrolysis experiments.

  2. Development of kinetic models for photoassisted electrochemical process using Ti/RuO2 anode and carbon nanotube-based O2-diffusion cathode

    International Nuclear Information System (INIS)

    Akbarpour, Amaneh; Khataee, Alireza; Fathinia, Mehrangiz; Vahid, Behrouz

    2016-01-01

    Highlights: • Preparation and characterization of carbon nanotube-based O 2 -diffusion cathode. • Photoassisted electrochemical process using Ti/RuO 2 anode and O 2 -diffusion cathode. • Degradation of C.I. Basic Yellow 28 under recirculation mode. • Development of kinetic models for photoassisted electrochemical process. - Abstract: A coupled photoassisted electrochemical system was utilized for degradation of C.I. Basic Yellow 28 (BY28) as a cationic azomethine dye under recirculation mode. Experiments were carried out by utilizing active titanium/ruthenium oxide (Ti/RuO 2 ) anode and O 2 -diffusion cathode with carbon nanotubes (CNTs). Transmission electron microscopy (TEM) image of the CNTs demonstrated that CNTs had approximately an inner and outer diameter of 5 nm and 19 nm, respectively. Then, the dye degradation kinetics was experimentally examined under various operational parameters including BY28 initial concentration (mg/L), current density (mA/cm 2 ), flow rate (L/h) and pH. Based on the generally accepted intrinsic elementary reactions for photoassisted electrochemical process (PEP), a novel kinetic model was proposed and validated for predicting the k app . The developed kinetic model explicitly describes the dependency of the k app on BY28 initial concentration and current density. A good agreement was obtained between the predicted values of k app and experimental results (correlation coefficient (R 2 ) = 0.996, mean squared error (MSE) = 2.10 × 10 −4 and mean absolute error (MAE) = 1.10 × 10 −2 ). Finally, in order to profoundly evaluate and compare the accuracy of the suggested intrinsic kinetic model, an empirical kinetic model was also developed as a function of main operational parameters, and an artificial neural network model (ANN) by 3-layer feed-forward back propagation network with topology of 5:9:1. The performance of the mentioned models was compared based on the error functions and analysis of variance (ANOVA). A

  3. Influence of the activator concentration on the kinetics of the alkaline activation process of a blast furnace slag

    Directory of Open Access Journals (Sweden)

    Fernández-Jiménez, A.

    1997-06-01

    Full Text Available The influence of activator solution concentration on hydration kinetics of an alkaline activated blast furnace slag has been studied. The alkaline activator used was a mix of waterglass (Na2SiO3∙nH2O and NaOH solution (of variable concentration. Final activator concentrations were 3,4 and 5 % Na2O wt. with respect to the slag total weight. Degree of reaction (α was determined from hydration heat values obtained through isothermal conduction calorimetry. From the results obtained it is deduced that a treshold value of 4 % Na2O wt. exists. For those concentrations and at test temperatures (except for 25ºC and 3 % Na2O wt., the mechanism controlling hydration reaction for a values higher than 0.5, is a diffusion process. This process is described by .Jander equation [D3=(1-(1-α1/32=(k/r2t=0,0426(t/t0,5]. The activation energy obtained for that process is of approximately 50-58 Kj/mol.

    Se ha estudiado la influencia de la concentración de la disolución activante en la cinética de hidratación de una escoria granulada de alto horno, activada alcalinamente a distintas temperaturas. El activador alcalino utilizado fue una mezcla de water glass (Na2SiO3∙nH2O con una disolución de NaOH (de concentración variable. Las concentraciones finales del activador alcalino fueron: 3, 4 y 5 % en peso de Na2O respecto a la masa total de escoria. El grado de reacción (α se determinó a partir de valores de calor de hidratación obtenidos por calorimetría de conducción isotérmica. De los resultados obtenidos se deduce que existe un valor umbral de concentraciones en torno al 4 % en peso de Na2O. También para dichas concentraciones y a las temperaturas de ensayo (excepto a 25ºC con un 3 % en peso de Na2O, el mecanismo que controla la reacción de hidrataci

  4. The interaction of C60 on Si(111 7x7 studied by Supersonic Molecular Beams: interplay between precursor kinetic energy and substrate temperature in surface activated processes.

    Directory of Open Access Journals (Sweden)

    Lucrezia eAversa

    2015-06-01

    Full Text Available Buckminsterfullerene (C60 is a molecule fully formed of carbon that can be used, owing to its electronic and mechanical properties, as clean precursor for the growth of carbon-based materials, ranging from -conjugated systems (graphenes to synthesized species, e.g. carbides such as silicon carbide (SiC. To this goal, C60 cage rupture is the main physical process that triggers material growth. Cage breaking can be obtained either thermally by heating up the substrate to high temperatures (630°C, after C60 physisorption, or kinetically by using Supersonic Molecular Beam Epitaxy (SuMBE techniques. In this work, aiming at demonstrating the growth of SiC thin films by C60 supersonic beams, we present the experimental investigation of C60 impacts on Si(111 7x7 kept at 500°C for translational kinetic energies ranging from 18 to 30 eV. The attained kinetically activated synthesis of SiC submonolayer films is probed by in-situ surface electron spectroscopies (XPS and UPS. Furthermore, in these experimental conditions the C60-Si(111 7×7 collision has been studied by computer simulations based on a tight-binding approximation to Density Functional Theory, DFT. Our theoretical and experimental findings point towards a kinetically driven growth of SiC on Si, where C60 precursor kinetic energy plays a crucial role, while temperature is relevant only after cage rupture to enhance Si and carbon reactivity. In particular, we observe a counterintuitive effect in which for low kinetic energy (below 22 eV, C60 bounces back without breaking more effectively at high temperature due to energy transfer from excited phonons. At higher kinetic energy (22 < K < 30 eV, for which cage rupture occurs, temperature enhances reactivity without playing a major role in the cage break. These results are in good agreement with ab-initio molecular dynamics simulations. SuMBE is thus a technique able to drive materials growth at low temperature regime.

  5. NEXAFS characterization and reactivity studies of bimetallic vanadium molybdenum oxynitride hydrotreating catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Kapoor, R.; Oyama, S.T. [Virginia Polytechnic Inst., Blacksburg, VA (United States); Fruehberger, B.; Chen, J.G. [Exxon Research and Engineering Company, Annandale, NJ (United States)

    1997-02-27

    The surface and bulk compositions of vanadium molybdenum oxynitride (V{sub 2}MoO{sub 1.7}N{sub 2.4}), prepared by temperature-programmed reaction (TPR) of vanadium molybdenum oxide (V{sub 2}MoO{sub 8}) with ammonia, have been characterized using near-edge X-ray absorption fine structure (NEXAFS) spectroscopy. The NEXAFS data were recorded at the K-edges of nitrogen and oxygen, the L-edge of vanadium, and the M-edge of molybdenum. The nitrogen K-edge region of V-Mo oxynitride shows the characteristic NEXAFS features of early-transition-metal nitrides, although these features are different from those of either VN or Mo{sub 2}N. Furthermore, comparison of the electron yield and fluorescence yield measurements also reveals that the oxidation state is different for vanadium near the surface region and for vanadium in the bulk, which is estimated to be 2.8 {+-} 0.3 and 3.8 {+-} 0.3, respectively. The oxidation state of bulk molybdenum is also estimated to be 4.4 {+-} 0.3. The X-ray diffraction pattern shows that the bulk phase of the bimetallic oxide is different from the pure monometallic oxide phases but the oxynitride has a cubic structure that resembles the pure vanadium and molybdenum nitride phases. The V-Mo oxide as prepared shows a preferential orientation of [001] crystallographic planes which is lost during the nitridation process. This shows that the solid state transformation V{sub 2}MoO{sub 8} {yields} V{sub 2}MoO{sub 1.7}N{sub 2.4} is not topotactic. 27 refs., 8 figs., 1 tab.

  6. Kinetics in radiation chemistry

    International Nuclear Information System (INIS)

    Hummel, A.

    1987-01-01

    In this chapter the authors first briefly review the kinetics of first- and second-order processes for continuous and pulsed irradiation, without taking the effects of nonhomogeneous formation of the species into consideration. They also discuss diffusion controlled reactions under conditions where interactions of more than two particles can be neglected, first the kinetics of the diffusion-controlled reaction of randomly generated species (homogeneous reaction) and then that of isolated pairs of reactants. The latter is often called geminate kinetics when dealing with pairs of oppositely charged species; they shall use this term for the kinetics of isolated pairs in general. In the last section they discuss briefly the kinetics of groups of more than two reactants

  7. Simultaneous influence of gas mixture composition and process temperature on Fe2O3->FeO reduction kinetics: neural network modeling

    Directory of Open Access Journals (Sweden)

    K. Piotrowski

    2005-09-01

    Full Text Available The kinetics of Fe2O3->FeO reaction was investigated. The thermogravimetric (TGA data covered the reduction of hematite both by pure species (nitrogen diluted CO or H2 and by their mixture. The conventional analysis has indicated that initially the reduction of hematite is a complex, surface controlled process, however once a thin layer of lower oxidation state iron oxides (magnetite, wüstite is formed on the surface, it changes to diffusion control. Artificial Neural Network (ANN has proved to be a convenient tool for modeling of this complex, heterogeneous reaction runs within the both (kinetic and diffusion regions, correctly considering influence of temperature and gas composition effects and their complex interactions. ANN's model shows the capability to mimic some extreme (minimum of the reaction rate within the determined temperature window, while the Arrhenius dependency is of limited use.

  8. Reaction network modelling for kinetic parameters of pyrolytic reactions of CHON extractants in nuclear fuel processing waste management. Contributed Paper IT-07

    International Nuclear Information System (INIS)

    Gaikar, Vilas G.; Thaore, Vaishali

    2014-01-01

    The recovery and purification of plutonium (Pu) from uranium (U) and of U from Thorium (Th) in spent nuclear fuel reprocessing is accomplished by processes that employ organophosphorous compounds as extractants.The main objective of the present work was to develop a suitable kinetic model and to determine the kinetic parameters of the set of reactions involved in the pyrolysis of amides by fitting the experimental data in the reaction network model. The experimental data and analysis are expected to be useful in the steam pyrolysis of amide waste in fuel reprocessing in the nuclear industry. The basic approach was to understand the reaction mechanism of the steam pyrolysis of amides and then to estimate the reaction rate constants for the generation and consumption of different species by solving the model equations, allowing for the determination of important species in the reaction network

  9. Modification of ntezi bentonite structure by hydrochloric acid: process kinetics and structural properties of the modified samples

    International Nuclear Information System (INIS)

    Ajemba, R.O.

    2014-01-01

    Bentonite from Ntezi was modified by reacting it with different concentrations of hydrochloric acid solutions. The modified samples were analysed by x-ray fluorescence. The kinetics of the modification reaction was studied by performing the experiment at different temperatures and times. Results of the analysis of the modified samples showed that the octahedral cations were removed which altered the chemical composition of the bentonite. The surface area and adsorptive capacity of the bentonite were improved after the modification. The kinetic studies showed that the acid modification reaction is controlled by the product layer diffusion and can be represented by (1-(l-X)/sup 1/3)/sup 2/ = k t; where, X is the fraction of the bentonite dissolved at time t. The activation energy was determined to be 24.98 kJ/mol. (author)

  10. Modeling of kinetics of the inducible protein complexes of the SOS system in bacteria E. coli which realize TLS process

    International Nuclear Information System (INIS)

    Belov, O.V.

    2008-01-01

    The mathematical model describing kinetics of the inducible genes of the protein complexes, formed during SOS response in bacteria Escherichia coli is developed. Within the bounds of developed approaches the auxiliary mathematical model describing changes in concentrations of the dimers, which are the components of final protein complexes, is developed. The solutions of both models are based on the experimental data concerning expression of the basic genes of the SOS system in bacteria Escherichia coli

  11. Adsorption behavior of direct red 80 and congo red onto activated carbon/surfactant: Process optimization, kinetics and equilibrium

    Science.gov (United States)

    Cheng, Zhengjun; Zhang, Lei; Guo, Xiao; Jiang, Xiaohui; Li, Tian

    2015-02-01

    Adsorptions of congo red and direct red 80 onto activated carbon/surfactant from aqueous solution were optimized. The Box-Behnken design (BBD) has been employed to analyze the effects of concentration of surfactant, temperature, pH, and initial concentration of the dye in the adsorption capacity. Their corresponding experimental data could be evaluated excellently by second order polynomial regression models and the two models were also examined based on the analysis of variance and t test statistics, respectively. The optimum conditions were obtained as follows: Cs = 34.10 μM, T = 50 °C, pH = 3.5, and CCR = 160 mg/L for the congo red system, and Cs = 34.10 μM, T = 50 °C, pH = 6.1, and CDR80 = 110 mg/L for the direct red 80 system. And in these conditions, the measured experimental maximum adsorption capacities for the congo red and direct red 80 removals were 769.48 mg/g and 519.90 mg/g, which were consistent with their corresponding predicted values, with small relative errors of -2.81% and -0.67%, respectively. The adsorption equilibrium and kinetics for the two dye adsorptions onto AC/DDAC were also investigated. The experimental data were fitted by four isotherm models, and Langmuir model presented the best fit. The kinetic studies indicated that the kinetic data followed the pseudo-second-order model.

  12. Process optimization and kinetics of biodiesel production from neem oil using copper doped zinc oxide heterogeneous nanocatalyst.

    Science.gov (United States)

    Gurunathan, Baskar; Ravi, Aiswarya

    2015-08-01

    Heterogeneous nanocatalyst has become the choice of researchers for better transesterification of vegetable oils to biodiesel. In the present study, transesterification reaction was optimized and kinetics was studied for biodiesel production from neem oil using CZO nanocatalyst. The highly porous and non-uniform surface of the CZO nanocatalyst was confirmed by AFM analysis, which leads to the aggregation of CZO nanoparticles in the form of multi layered nanostructures. The 97.18% biodiesel yield was obtained in 60min reaction time at 55°C using 10% (w/w) CZO nanocatalyst and 1:10 (v:v) oil:methanol ratio. Biodiesel yield of 73.95% was obtained using recycled nanocatalyst in sixth cycle. The obtained biodiesel was confirmed using GC-MS and (1)H NMR analysis. Reaction kinetic models were tested on biodiesel production, first order kinetic model was found fit with experimental data (R(2)=0.9452). The activation energy of 233.88kJ/mol was required for transesterification of neem oil into biodiesel using CZO nanocatalyst. Copyright © 2015 Elsevier Ltd. All rights reserved.

  13. Solar photo-Fenton process on the abatement of antibiotics at a pilot scale: Degradation kinetics, ecotoxicity and phytotoxicity assessment and removal of antibiotic resistant enterococci.

    Science.gov (United States)

    Michael, I; Hapeshi, E; Michael, C; Varela, A R; Kyriakou, S; Manaia, C M; Fatta-Kassinos, D

    2012-11-01

    This work investigated the application of a solar driven advanced oxidation process (solar photo-Fenton), for the degradation of antibiotics at low concentration level (μg L(-1)) in secondary treated domestic effluents at a pilot-scale. The examined antibiotics were ofloxacin (OFX) and trimethoprim (TMP). A compound parabolic collector (CPC) pilot plant was used for the photocatalytic experiments. The process was mainly evaluated by a fast and reliable analytical method based on a UPLC-MS/MS system. Solar photo-Fenton process using low iron and hydrogen peroxide doses ([Fe(2+)](0) = 5 mg L(-1); [H(2)O(2)](0) = 75 mg L(-1)) was proved to be an efficient method for the elimination of these compounds with relatively high degradation rates. The photocatalytic degradation of OFX and TMP with the solar photo-Fenton process followed apparent first-order kinetics. A modification of the first-order kinetic expression was proposed and has been successfully used to explain the degradation kinetics of the compounds during the solar photo-Fenton treatment. The results demonstrated the capacity of the applied advanced process to reduce the initial wastewater toxicity against the examined plant species (Sorghum saccharatum, Lepidium sativum, Sinapis alba) and the water flea Daphnia magna. The phytotoxicity of the treated samples, expressed as root growth inhibition, was higher compared to that observed on the inhibition of seed germination. Enterococci, including those resistant to OFX and TMP, were completely eliminated at the end of the treatment. The total cost of the full scale unit for the treatment of 150 m(3) day(-1) of secondary wastewater effluent was found to be 0.85 € m(-3). Copyright © 2012 Elsevier Ltd. All rights reserved.

  14. Removal of Dibenzothiophene Using Activated Carbon/γ-Fe2O3 Nano-Composite: Kinetic and Thermodynamic Investigation of the Removal Process

    Directory of Open Access Journals (Sweden)

    Maryam Fayazi

    2015-12-01

    Full Text Available In the present study, removal of dibenzothiophene (DBT from model oil (n-hexane was investigated using magnetic activated carbon (MAC nano-composite adsorbent. The synthesized nano-composite was characterized by FT-IR, FE-SEM, BET and VSM techniques. The MAC nano-composite exhibited a nearly superparamagnetic property with a saturation magnetization (Ms of 29.2 emu g-1, which made it desirable for separation under an external magnetic field. The magnetic adsorbent afforded a maximum adsorption capacity of 38.0 mg DBT g-1 at the optimized conditions (adsorbent dose, 8 g l-1; contact time, 1 h; temperature, 25 °C. Langmuir, Freundlich and Temkin isotherm models were used to fit equilibrium data for MAC nano-composite. Adsorption process could be well described by the Langmuir model. Kinetic studies were carried out and showed the sorption kinetics of DBT was best described by a pseudo-second-order kinetic model. In addition, the MAC nano-composite exhibited good capability of recycling to adsorb DBT in gasoline deep desulfurization.

  15. Physical kinetics

    International Nuclear Information System (INIS)

    Lifschitz, E.M.; Pitajewski, L.P.

    1983-01-01

    The textbook covers the subject under the following headings: kinetic gas theory, diffusion approximation, collisionless plasma, collisions within the plasma, plasma in the magnetic field, theory of instabilities, dielectrics, quantum fluids, metals, diagram technique for nonequilibrium systems, superconductors, and kinetics of phase transformations

  16. Thermodynamic-state and kinetic-process dependent dual ferromagnetic states in high-Si content FeMn(PSi) alloys

    International Nuclear Information System (INIS)

    Li, Guijiang; Eriksson, Olle; Johansson, Börje; Vitos, Levente

    2015-01-01

    We have found that thermodynamic state and kinetic process co-determine the dual ferromagnetic (FM) orders in high-Si content FeMnP 1−x Si x (0.25 < x < 0.5). Alloys undergoing high temperature annealing and quenching process prefer a high magnetic moment FM state in a chemically partial disordered structure with low c/a ratio. This mechanism is suggested to be responsible for the often discussed virgin effect as well. A chemically ordered structure obtained by a slow cooling process from a relatively low annealing temperature and the increase in Si content stabilize a metastable lattice with high c/a ratio and FM order with low magnetic moment. The non-simultaneity of the magnetic and structural transitions can be responsible for the occurrence of FM state in the high c/a range. Thus, a c/a ratio that changes from high to low is physically plausible to stabilize the metastable FM order at low temperature. Our theoretical observations indicate that suitable thermodynamic state and kinetic diffusion process is crucial for optimizing magnetocaloric properties and exploring feasible magnetocaloric materials

  17. Dissipation kinetics, safety evaluation, and assessment of pre-harvest interval (PHI) and processing factor for kresoxim methyl residues in grape.

    Science.gov (United States)

    Sabale, Rupali; Shabeer, T P Ahammed; Utture, Sagar C; Banerjee, Kaushik; Jadhav, Manjusha R; Oulkar, Dasharath P; Adsule, Pandurang G; Deshmukh, Madhukar B

    2014-04-01

    A field dissipation study was conducted to evaluate the pre-harvest interval (PHI) and processing factor (PF) for kresoxim methyl (Ergon 44.3 SC) residues in grapes and during raisin making process at recommended dose (RD) and double the recommended dose (DRD). Kresoxim methyl residues dissipated following 1st-order kinetics with a half-life of 10 and 18 days at RD and DRD, respectively. The PHIs with respect to the European Union maximum residue limit (EU-MRL) of 1 mg kg(-1) for grapes were 13 and 30 days at RD and DRD, respectively. The degradation data during grape to raisin making process were best fitted to nonlinear 1st + 1st-order kinetics with a half-life ranging between 4 and 8 days for both shade drying and with raisin dryer at different doses. The PFs were 1.19 and 1.24 with shade drying and 1.09 and 1.10 with raisin dryer, respectively, which indicates concentration of the residues during raisin making process. The dietary exposure of kresoxim methyl on each sampling day was less than the respective maximum permissible intake both at RD and DRD. The residues of kresoxim methyl in market samples of grapes and raisins were well below the EU-MRL and were also devoid of any risk of acute toxicity related to dietary exposure.

  18. Influence of various irradiation processes on the mechanical properties and polymerisation kinetics of bulk-fill resin based composites.

    Science.gov (United States)

    Ilie, Nicoleta; Keßler, Andreas; Durner, Jürgen

    2013-08-01

    To assess the effect of irradiation time and distance of the light tip on the micro-mechanical properties and polymerisation kinetics of two bulk-fill resin-based composites at simulated clinically relevant filling depth. Micro-mechanical properties (Vickers hardness (HV), depth of cure (DOC) and indentation modulus (E)) and polymerisation kinetics (real-time increase of degree of cure (DC)) of two bulk-fill resin-based composites (Tetric EvoCeram(®) Bulk Fill, Ivoclar Vivadent and x-tra base, Voco) were assessed at varying depth (0.1-6mm in 100μm steps for E and HV and 0.1, 2, 4 and 6mm for DC), irradiation time (10, 20 or 40s, Elipar Freelight2) and distances from the light tip (0 and 7mm). Curing unit's irradiance was monitored in 1mm steps at distances up to 10mm away from the light tip on a laboratory-grade spectrometer. Multivariate analysis (α=0.05), Student's t-test and Pearson correlation analysis were considered. The influence of material on the measured mechanical properties was significant (η(2)=0.080 for E and 0.256 for HV), while the parameters irradiation time, distance from the light tip and depth emphasise a stronger influence on Tetric EvoCeram(®) Bulk Fill. The polymerisation kinetics could be described by an exponential sum function, distinguishing between the gel and the glass phase. The above mentioned parameters strongly influenced the start of polymerisation (gel phase), and were of less importance for the glass phase. Both materials enable at least 4mm thick increments to be cured in one step under clinically relevant curing conditions. The susceptibility to variation in irradiance was material dependent, thus properties measured under clinically simulated curing conditions might vary to a different extent from those measured under ideal curing conditions. Copyright © 2013 Elsevier Ltd. All rights reserved.

  19. Heparin kinetics

    International Nuclear Information System (INIS)

    Swart, C.A.M. de.

    1983-01-01

    The author has studied the kinetics of heparin and heparin fractions after intravenous administration in humans and in this thesis the results of this study are reported. Basic knowledge about the physico-chemical properties of heparin and its interactions with proteins resulting in anticoagulant and lipolytic effects are discussed in a review (chapter II), which also comprises some clinical aspects of heparin therapy. In chapter III the kinetics of the anticoagulant effect are described after intravenous administration of five commercial heparin preparations. A mathematical model is presented that fits best to these kinetics. The kinetics of the anticoagulant and lipolytic effects after intravenous injection of various 35 S-radiolabelled heparin fractions and their relationship with the disappearance of the radiolabel are described in chapter IV. Chapter V gives a description of the kinetics of two radiolabels after injection of in vitro formed complexes consisting of purified, 125 I-radiolabelled antithrombin III and various 35 S-radiolabelled heparin fractions. (Auth.)

  20. Comparison of three combined sequencing batch reactor followed by enhanced Fenton process for an azo dye degradation: Bio-decolorization kinetics study

    Energy Technology Data Exchange (ETDEWEB)

    Azizi, A., E-mail: armina_84@yahoo.com [Civil and Environmental Engineering Department, Amirkabir University of Technology, Hafez Ave., Tehran15875-4413 (Iran, Islamic Republic of); Alavi Moghaddam, M.R., E-mail: alavim@yahoo.com [Civil and Environmental Engineering Department, Amirkabir University of Technology, Hafez Ave., Tehran15875-4413 (Iran, Islamic Republic of); Maknoon, R., E-mail: rmaknoon@yahoo.com [Civil and Environmental Engineering Department, Amirkabir University of Technology, Hafez Ave., Tehran15875-4413 (Iran, Islamic Republic of); Kowsari, E., E-mail: kowsarie@aut.ac.ir [Department of Chemistry, Amirkabir University of Technology, Hafez Ave., Tehran 15875-4413 (Iran, Islamic Republic of)

    2015-12-15

    Highlights: • Three combined advanced SBR and enhanced Fenton process as post treatment was compared. • Higher biomass concentration, dye, COD and metabolites removal was presented together. • Pseudo zero and pseudo first-order bio-decolorization kinetics were observed in all SBRs. • High reduction of AR18 to intermediate metabolites was monitored by HPLC. - Abstract: The purpose of this research was to compare three combined sequencing batch reactor (SBR) – Fenton processes as post-treatment for the treatment of azo dye Acid Red 18 (AR18). Three combined treatment systems (CTS1, CTS2 and CTS3) were operated to investigate the biomass concentration, COD removal, AR18 dye decolorization and kinetics study. The MLSS concentration of CTS2 reached 7200 mg/L due to the use of external feeding in the SBR reactor of CTS2. The COD concentration remained 273 mg/L and 95 mg/L (initial COD = 3270 mg/L) at the end of alternating anaerobic–aerobic SBR with external feeding (An-A MSBR) and CTS2, respectively, resulting in almost 65% of Fenton process efficiency. The dye concentration of 500 mg/L was finally reduced to less than 10 mg/L in all systems indicating almost complete AR18 decolorization, which was also confirmed by UV–vis analysis. The dye was removed following two successive parts as parts 1 and 2 with pseudo zero-order and pseudo first-order kinetics, respectively, in all CTSs. Higher intermediate metabolites degradation was obtained using HPLC analysis in CTS2. Accordingly, a combined treatment system can be proposed as an appropriate and environmentally-friendly system for the treatment of the azo dye AR18 in wastewater.

  1. Impact of processing conditions on the kinetic of vitamin C degradation and 2-furoylmethyl amino acid formation in dried strawberries.

    Science.gov (United States)

    Gamboa-Santos, Juliana; Megías-Pérez, Roberto; Soria, A Cristina; Olano, Agustín; Montilla, Antonia; Villamiel, Mar

    2014-06-15

    In this paper, a study on the usefulness of the determination of vitamin C together with indicators of the initial steps of Maillard reaction (2-furoylmethyl amino acids, 2-FM-AA) during the convective drying of strawberries has been carried out for the first time, paying special attention to the kinetics of degradation and formation, respectively, of both parameters. Formation of 2-FM-AA of Lys, Arg and GABA and vitamin C loss increased with time and temperature following, respectively, a zero and first-order kinetics. As supported by its lower activation energy, 2-FM-GABA (55.9 kJ/mol) and 2-FM-Lys+2-FM-Arg (58.2 kJ/mol) were shown to be slightly more sensitive indicators than vitamin C (82.1 kJ/mol). The obtained results, together with a complementary study on the rehydration ability and sensorial attributes of samples, pointed out the suitability of the convective drying system to obtain dried strawberries of high nutritive quality and bioactivity and good consumer acceptance. Copyright © 2013 Elsevier Ltd. All rights reserved.

  2. Degradation of the fungicide carbendazim in aqueous solutions with UV/TiO{sub 2} process: Optimization, kinetics and toxicity studies

    Energy Technology Data Exchange (ETDEWEB)

    Saien, J. [Department of Applied Chemistry, Bu-Ali Sina University, Hamedan 65174 (Iran, Islamic Republic of)], E-mail: saien@basu.ac.ir; Khezrianjoo, S. [Department of Applied Chemistry, Bu-Ali Sina University, Hamedan 65174 (Iran, Islamic Republic of)

    2008-09-15

    An attempt was made to investigate the potential of UV-photocatalytic process in the presence of TiO{sub 2} particles for the degradation of carbendazim (C{sub 9}H{sub 9}N{sub 3}O{sub 2}), a fungicide with a high worldwide consumption but considered as a 'priority hazard substance' by the Water Framework Directive of the European Commission (WFDEC). A circulating upflow photo-reactor was employed and the influence of catalyst concentration, pH and temperature were investigated. The results showed that degradation of this fungicide can be conducted in the both processes of only UV-irradiation and UV/TiO{sub 2}; however, the later provides much better results. Accordingly, a degradation of more than 90% of fungicide was achieved by applying the optimal operational conditions of 70 mg L{sup -1} of catalyst, natural pH of 6.73 and ambient temperature of 25 deg. C after 75 min irradiation. Under these mild conditions, the initial rate of degradation can be described well by the Langmuir-Hinshelwood kinetic model. Toxicological assessments on the obtained samples were also performed by measurement of the mycelium growth inhibition of Fusarium oxysporum fungus on PDA medium. The results indicate that the kinetics of degradation and toxicity are in reasonably good agreement mainly after 45 min of irradiation; confirming the effectiveness of photocatalytic process.

  3. Modifying an Active Compound’s Release Kinetic Using a Supercritical Impregnation Process to Incorporate an Active Agent into PLA Electrospun Mats

    Directory of Open Access Journals (Sweden)

    Carol López de Dicastillo

    2018-04-01

    Full Text Available The main objective of this work was to study the release of cinnamaldehyde (CIN from electrospun poly lactic acid (e-PLA mats obtained through two techniques: (i direct incorporation of active compound during the electrospinning process (e-PLA-CIN; and (ii supercritical carbon dioxide (scCO2 impregnation of CIN within electrospun PLA mats (e-PLA/CINimp. The development and characterization of both of these active electrospun mats were investigated with the main purpose of modifying the release kinetic of this active compound. Morphological, structural, and thermal properties of these materials were also studied, and control mats e-PLA and e- PLA CO 2 were developed in order to understand the effect of electrospinning and scCO2 impregnation, respectively, on PLA properties. Both strategies of incorporation of this active compound into PLA matrix resulted in different morphologies that influenced chemical and physical properties of these composites and in different release kinetics of CIN. The electrospinning and scCO2 impregnation processes and the presence of CIN altered PLA thermal and structural properties when compared to an extruded PLA material. The incorporation of CIN through scCO2 impregnation resulted in higher release rate and lower diffusion coefficients when compared to active electrospun mats with CIN incorporated during the electrospinning process.

  4. Hydroprocessing to produce reformulated Gasolines. The ISAL{sup TM} process

    Energy Technology Data Exchange (ETDEWEB)

    Antos, G.J. [UOP, Des Plaines, IL (United States); Solari, B.; Monque, R. [Intevep S.A., Caracas (Venezuela)

    1997-07-01

    As a result of forthcoming environmental regulations, such as those established in the U.S. Clean Air Act, petroleum refiners around the world are searching for low-investment solutions to accomplish hydroprocessing requirements. These regulations are expressed in the Complex Model, which brings together sulfur content, olefin content, vapor pressure, and boiling range in an interactive fashion. Processes need to successfully reduce these pollutants and still maintain high yields of high octane-product. Because FCC naphta accounts for 90 % of the sulfur and olefins in the entire gasoline pool, hydrotreating this material is an attractive process alternative, provided that octane losses are minimized. The ISAL{sup TM} process, jointly developed by INTEVEP, S.A., and UOP, is a selective hydrotreating process to improve naphta quality by reducing sulfur, nitrogen, and olefins without octane loss. The paper discusses aspects of the process and catalyst chemistries leading to these desirable results. 6 refs.

  5. Kinetic processes in a laser-heated helium--nitrogen plasma for use as a uv laser medium

    International Nuclear Information System (INIS)

    Brown, R.T.

    1975-01-01

    Experimental and theoretical studies of an optically pumped electric discharge laser in helium-nitrogen mixtures are described. While the inherent efficiency of this system is rather low, these studies illustrate the basic parameters controlling the dynamics and efficiency of such a laser. In the experiments, intense diffuse discharges were obtained at pressures up to 12 atm and amplified spontaneous emission along the axis of the discharge was observed. The numerical modeling studies showed qualitative agreement with the experimental data and gave an optimized value of the kinetic coupling efficiency (absorbed 10.6-μ power to uv laser power) of 1.6% and of the total efficiency (energy stored in the TEA laser supply to uv output energy) of 0.1 to 0.2%

  6. Kinetics and mechanisms of metal retention/release in geochemical processes in soil. 1997 annual progress report

    International Nuclear Information System (INIS)

    Taylor, R.W.

    1997-01-01

    'Remediation of soils polluted with heavy metals is a major challenge facing the nation. This is especially so at many DOE facilities and other superfund sites. In many cases, speciation of the metals is inaccurate and difficult and the mechanisms by which the metals are retained/released in soils over long times are poorly understood. Consequently, the long-term fate of metals in soils cannot be precisely predicted and often, the remediation recommendations and techniques that are employed to clean up soils may be ineffective or unnecessary. Accordingly, the authors are proposing work to generate basic knowledge on the kinetics and mechanism(s) of heavy metal retention/release by soil mineral colloids as affected by inorganic anion. The nature of the interaction of Cd(II), Co(II), Cr(VI), Cu(II), Ni(II) and Pb(II) with pure soil minerals and extracted soil clays will be investigated. The colloids will be characterized in terms of surface area, surface charge and surface site density. They will be used to study the effect(s) of pH, phosphate rate, and temperature on metals retention/release. The experiments will involve using various kinetic and isothermic sorption equations as models to describe the data thus acquired. The spectroscopic methods will involve using extended x-ray absorption fine structure spectroscopy (EXAFS) and Fourier Transform Infrared Spectroscopy (FTIR). The data generated from the proposed study will assist in designing better remediation strategies to effectively clean up toxic heavy metal contaminated soils at DOE facilities and other superfund sites.'

  7. Kinetic Interface

    DEFF Research Database (Denmark)

    2009-01-01

    A kinetic interface for orientation detection in a video training system is disclosed. The interface includes a balance platform instrumented with inertial motion sensors. The interface engages a participant's sense of balance in training exercises.......A kinetic interface for orientation detection in a video training system is disclosed. The interface includes a balance platform instrumented with inertial motion sensors. The interface engages a participant's sense of balance in training exercises....

  8. The kinetics of activation and deactivation in the process of water ozonising used for advanced oxidation of the dust waste from moulding sands

    Directory of Open Access Journals (Sweden)

    A. Baliński

    2009-01-01

    Full Text Available Adding coal dust and organic carriers of the lustrous carbon to bentonite-bonded moulding sands in amounts justified by thetechnological regime and the use of cores and protective coatings based on organic compounds create serious threats to the environment.During thermal destruction of the individual components of moulding and core sands, some toxic organic compounds are emitted. They formthe majority of the Hazardous Air Pollutants (HAPs, and include mainly compounds like benzene, toluene, xylene, naphtalene, hexane,acetaldehyde, acrolein, aniline, cresol and cumene, their polycyclic derivatives, phenol, formaldehyde, and other similar matters. In thusformed dust waste, the amount of which constitutes about 20% of all the waste from foundries using traditional moulding and core sands, there are still full-value materials which can undergo total recycling, providing the HAPs are partially or totally removed from them. The article discusses some problems of the advanced oxidation of selected toxic chemical compounds present in bentonite-bonded moulding sands due to the effect of high temperature. The results of the investigations of the kinetics of the process of maximum water saturation with ozone (acting as an oxidiser and of the kinetics of the natural process of ozone decomposition to diatomic oxygen were presented. It has been stated that the maximum time of water saturation with ozone using an OZOMATIC OSC-MODULAR 4HC ozone generator and a 1m3 capacity tank with water is 60 minutes. After 30 minute break in the ozonising process, the ozone concentration in water decreases by 40 to 50%. To obtain maximum ozone concentration in water during the next ozonising cycle, it is necessary to have the ozone-generating device running for the next 30 minutes. The stabilisation of ozone concentration in water takes place only after the third ozonising cycle, when it reaches nearly 80%of the maximum value obtained after the first process cycle

  9. Process optimization and analysis of product inhibition kinetics of crude glycerol fermentation for 1,3-Dihydroxyacetone production.

    Science.gov (United States)

    Dikshit, Pritam Kumar; Padhi, Susant Kumar; Moholkar, Vijayanand S

    2017-11-01

    In present study, statistical optimization of biodiesel-derived crude glycerol fermentation to DHA by immobilized G. oxydans cells over polyurethane foam is reported. Effect of DHA (product) inhibition on crude glycerol fermentation was analyzed using conventional biokinetic models and new model that accounts for both substrate and product inhibition. Optimum values of fermentation parameters were: pH=4.7, temperature=31°C, initial substrate concentration=20g/L. At optimum conditions, DHA yield was 89% (17.83g/L). Effect of product inhibition on fermentation was trivial for DHA concentrations ≤30g/L. At higher concentrations (≥50g/L), kinetics and yield of fermentation showed marked reduction with sharp drop in V max and K S values. Inhibition effect was more pronounced for immobilized cells due to restricted transport of fermentation mixture across polyurethane foam. Retention of fermentation mixture in immobilized matrix resulted in higher localized DHA concentration that possibly enhanced inhibition effect. Copyright © 2017 Elsevier Ltd. All rights reserved.

  10. Modeling the kinetics nonenzymatic browning reactions and rheological behavior in the termal process of fruit juices and pulps

    Directory of Open Access Journals (Sweden)

    Damian Manayay

    2010-06-01

    Full Text Available In the manufacture of fruit juices and pulps, is of paramount importance to refer to non-enzymatic browning and rheological behavior. The non-enzymatic browning is a phenomenon of darkening of a purely chemical (Braverman, 1980, is characterized by the presence of brown polymers called melanoidins, generated by the Maillard reaction or condensation of melanoidins, the caramelization and degradation of acid ascorbic, while the rheological behavior is define as the proportion deformation of the material when exposed to shear stress (σ caused by a rheometer (Muller, 1978; Ibarz, 2005. Modeling studies of colour formation and definition of rheological behavior, considered in this review, aimed at the conclusion of the existence of a zero kinetic and first order respectively, and the most influential factors with the reactions are mainly Maillard, temperature, amino acids presence, water activity and pH, while the rheological behavior is affected by temperature, solid concentration and particles size that make up the suspension in the specific case of the pulps.

  11. Radiation processed polychloroprene-co-ethylene-propene diene terpolymer blends: Effect of radiation vulcanization on solvent transport kinetics

    Energy Technology Data Exchange (ETDEWEB)

    Dubey, K.A. [Radiation Technology Development Section, Bhabha Atomic Research Centre, Room No. S-1, HIRUP Building, Trombay, Mumbai 400 085 (India); Bhardwaj, Y.K. [Radiation Technology Development Section, Bhabha Atomic Research Centre, Room No. S-1, HIRUP Building, Trombay, Mumbai 400 085 (India)], E-mail: ykbhard@barc.gov.in; Chaudhari, C.V.; Kumar, Virendra; Goel, N.K.; Sabharwal, S. [Radiation Technology Development Section, Bhabha Atomic Research Centre, Room No. S-1, HIRUP Building, Trombay, Mumbai 400 085 (India)

    2009-03-15

    Blends of polychloroprene rubber (PCR) and ethylene propylene diene terpolymer rubber (EPDM) of different compositions were made and exposed to different gamma radiation doses. The radiation sensitivity and radiation vulcanization efficiency of blends was estimated by gel-content analysis, Charlesby-Pinner parameter determination and crosslinking density measurements. Gamma radiation induced crosslinking was most efficient for EPDM (p{sub 0}/q{sub 0} {approx} 0.08), whereas it was the lowest for blends containing 40% PCR (p{sub 0}/q{sub 0} {approx} 0.34). The vulcanized blends were characterized for solvent diffusion characteristics by following the swelling dynamics. Blends with higher PCR content showed anomalous swelling. The sorption and permeability of the solvent were not strictly in accordance with each other and the extent of variation in two parameters was found to be a function of blend composition. The {delta}G values for solvent diffusion were in the range -2.97 to -9.58 kJ/mol and indicated thermodynamically favorable sorption for all blends. These results were corroborated by dynamic swelling, experimental as well as simulated profiles and have been explained on the basis of correlation between crosslinking density, diffusion kinetics, thermodynamic parameters and polymer-polymer interaction parameter.

  12. Chemical kinetics of gas reactions

    CERN Document Server

    Kondrat'Ev, V N

    2013-01-01

    Chemical Kinetics of Gas Reactions explores the advances in gas kinetics and thermal, photochemical, electrical discharge, and radiation chemical reactions. This book is composed of 10 chapters, and begins with the presentation of general kinetic rules for simple and complex chemical reactions. The next chapters deal with the experimental methods for evaluating chemical reaction mechanisms and some theories of elementary chemical processes. These topics are followed by discussions on certain class of chemical reactions, including unimolecular, bimolecular, and termolecular reactions. The rema

  13. Contribution to the identification of the processes kinetically limiting of the zirconium alloys oxidation; characterization of the oxide films formed at high temperature by solids electrochemistry

    International Nuclear Information System (INIS)

    Vermoyal, J.J.

    2000-06-01

    The corrosion behavior of zirconium alloys used for cladding tubes has been extensively studied under several oxidation conditions (temperature, steam, dry air, oxygen...) in order to clarify the mechanism(s) of oxide growth and breakdown. Oxidation rate is generally assumed to be controlled by oxygen diffusion inwards the oxide layer. Nevertheless, several experimental facts, such as acceleration or inhibition of corrosion rate in coupling conditions, suggest that electrochemical processes are involved as a rate determining step. This work is an attempt to shed light about the rate-limiting-mechanism of two zirconium alloys oxidation: Zircaloy-4 (Zy-4) and Zr-Nb(1%)O(0,13%). Impedance spectroscopy characterizations of oxide films formed in high temperature water and studied in gaseous atmosphere clearly show the difference of electrical properties between the two alloys. The in situ electrochemical and thermogravimetric investigations in gaseous medium, and the polarization effects on oxidation and hydridation of Zr alloys in PWRs conditions indicate that oxygen diffusion can be considered as the limiting kinetic step for Zy-4 oxidation. On the contrary, the acceleration of oxide growth on Zr-Nb(1%)O(0,13%) under anodic polarization in PWRs conditions (360 deg C) suggests that either the electronic conductivity in the oxide or an interfacial process at least partially control the oxidation rate. Catalytic effects observed in gaseous medium when noble metals increase the oxygen reduction rate would tend to corroborate the oxidation control of this alloy by an interfacial mechanism. An electrochemical description and a heterogeneous kinetics approach based on a diffusion-interfacial process as rate determining step are then proposed. (author)

  14. Impact of pH and Total Soluble Solids on Enzyme Inactivation Kinetics during High Pressure Processing of Mango (Mangifera indica) Pulp.

    Science.gov (United States)

    Kaushik, Neelima; Nadella, Tejaswi; Rao, P Srinivasa

    2015-11-01

    This study was undertaken with an aim to enhance the enzyme inactivation during high pressure processing (HPP) with pH and total soluble solids (TSS) as additional hurdles. Impact of mango pulp pH (3.5, 4.0, 4.5) and TSS (15, 20, 25 °Brix) variations on the inactivation of pectin methylesterase (PME), polyphenol oxidase (PPO), and peroxidase (POD) enzymes were studied during HPP at 400 to 600 MPa pressure (P), 40 to 70 °C temperature (T), and 6- to 20-min pressure-hold time (t). The enzyme inactivation (%) was modeled using second order polynomial equations with a good fit that revealed that all the enzymes were significantly affected by HPP. Response surface and contour models predicted the kinetic behavior of mango pulp enzymes adequately as indicated by the small error between predicted and experimental data. The predicted kinetics indicated that for a fixed P and T, higher pulse pressure effect and increased isobaric inactivation rates were possible at lower levels of pH and TSS. In contrast, at a fixed pH or TSS level, an increase in P or T led to enhanced inactivation rates, irrespective of the type of enzyme. PPO and POD were found to have similar barosensitivity, whereas PME was found to be most resistant to HPP. Furthermore, simultaneous variation in pH and TSS levels of mango pulp resulted in higher enzyme inactivation at lower pH and TSS during HPP, where the effect of pH was found to be predominant than TSS within the experimental domain. Exploration of additional hurdles such as pH, TSS, and temperature for enzyme inactivation during high pressure processing of fruits is useful from industrial point of view, as these parameters play key role in preservation process design. © 2015 Institute of Food Technologists®

  15. Tolfenamic acid degradation by direct photolysis and the UV-ABC/H2O2 process: factorial design, kinetics, identification of intermediates, and toxicity evaluation.

    Science.gov (United States)

    de Melo da Silva, Lucas; Pereira Cavalcante, Rodrigo; Fabbro Cunha, Rebeca; Gozzi, Fábio; Falcao Dantas, Renato; de Oliveira, Silvio Cesar; Machulek, Amilcar

    2016-12-15

    This study employed direct UV-ABC photolysis and the UV-ABC/H 2 O 2 process to investigate the degradation of tolfenamic acid (TA), a common anti-inflammatory drug used in both human and veterinary medicine. A 2 3 factorial design with added center point was used to evaluate the effect of three independent variables-namely, H 2 O 2 concentration ([H 2 O 2 ]), TA concentration ([TA]), and experiment time (time)-on TA degradation and H 2 O 2 photolysis during UV-ABC/H 2 O 2 treatment using a high-pressure mercury vapor lamp (photon flux of 2.6307 × 10 4 J s -1 ) as the UV irradiation source. The responses yielded similar values, revealing a linear behavior, with correlation coefficients R = 0.9968 and R adj = 0.9921 for TA degradation and R = 0.9828 and R adj = 0.9570 for H 2 O 2 photolysis. The most efficient combination of variables was [H 2 O 2 ] = 255 mg L -1 and [TA] = 25 mg L -1 , resulting in 100% TA degradation and 98.87% H 2 O 2 photolysis by 90 min of treatment. Additionally, the second-order kinetic constant of the reaction between TA and HO ● was determined using a competitive kinetic model, employing 2,4-dichlorophenoxyacetic acid (2,4D) as the reference compound. The kinetic constant was 1.9 × 10 10 M -1 s -1 in alkaline medium. TA degradation by direct photolysis generated quinone imines as by-products, responsible for the formation of a dark red "internal filter" that increased the value of acute toxicity to Artemia salina. The UV-ABC/H 2 O 2 process did not promote formation of quinone imines by 90 min of treatment and therefore did not increase acute toxicity values. Several by-products generated during TA degradation were identified and possible degradation pathways for the UV-ABC and UV-ABC/H 2 O 2 processes were proposed. Copyright © 2016 Elsevier B.V. All rights reserved.

  16. Process optimization and kinetics for leaching of rare earth metals from the spent Ni-metal hydride batteries.

    Science.gov (United States)

    Meshram, Pratima; Pandey, B D; Mankhand, T R

    2016-05-01

    Nickel-metal hydride batteries (Ni-MH) contain not only the base metals, but valuable rare earth metals (REMs) viz. La, Sm, Nd, Pr and Ce as well. In view of the importance of resource recycling and assured supply of the contained metals in such wastes, the present study has focussed on the leaching of the rare earth metals from the spent Ni-MH batteries. The conditions for the leaching of REMs from the spent batteries were optimized as: 2M H2SO4, 348K temperature and 120min of time at a pulp density (PD) of 100g/L. Under this condition, the leaching of 98.1% Nd, 98.4% Sm, 95.5% Pr and 89.4% Ce was achieved. Besides the rare earth metals, more than 90% of base metals (Ni, Co, Mn and Zn) were also leached out in this condition. Kinetic data for the dissolution of all the rare earth metals showed the best fit to the chemical control shrinking core model. The leaching of metals followed the mechanism involving the chemical reaction proceeding on the surface of particles by the lixiviant, which was corroborated by the XRD phase analysis and SEM-EDS studies. The activation energy of 7.6, 6.3, 11.3 and 13.5kJ/mol was acquired for the leaching of neodymium, samarium, praseodymium and cerium, respectively in the temperature range 305-348K. From the leach liquor, the mixed rare earth metals were precipitated at pH∼1.8 and the precipitated REMs was analyzed by XRD and SEM studies to determine the phases and the morphological features. Copyright © 2015. Published by Elsevier Ltd.

  17. Oxidation of microcystin-LR by the Fenton process : Kinetics, degradation intermediates, water quality and toxicity assessment

    NARCIS (Netherlands)

    Park, Jeong-Ann; Yang, Boram; Park, Chanhyuk; Choi, Jae-Woo; van Genuchten, Case M.|info:eu-repo/dai/nl/413489647; Lee, Sang-Hyup

    2017-01-01

    The Fenton process was assessed as a cost-effective technology for the removal of Microcystin-LR (MC-LR) among UV, UV/H2O2, and Fenton process according to efficiency and electrical energy per order (EE/O). The determined practical concentrations of the Fenton reagents were 5 mg/L Fe(II) and 5 mg/L

  18. Granulocyte kinetics

    International Nuclear Information System (INIS)

    Peters, A.M.; Lavender, J.P.; Saverymuttu, S.H.

    1985-01-01

    By using density gradient materials enriched with autologous plasma, the authors have been able to isolate granulocutes from other cellular elements and label them with In-111 without separation from a plasma environment. The kinetic behavior of these cells suggests that phenomena attributed to granulocyte activation are greatly reduced by this labeling. Here, they review their study of granulocyte kinetics in health and disease in hope of quantifying sites of margination and identifying principal sites of destruction. The three principle headings of the paper are distribution, life-span, and destruction

  19. Evaluation of Chemical Kinetic for Mathematics Model Reduction of Cadmium Reaction Rate, Constant and Reaction Orde in to Electrochemical Process

    International Nuclear Information System (INIS)

    Prayitno

    2007-01-01

    The experiment was reduction of cadmium rate with electrochemical influenced by time process, concentration, current strength and type of electrode plate. The aim of the experiment was to know the influence, mathematic model reduction of cadmium the reaction rate, reaction rate constant and reaction orde influenced by time process, concentration, current strength and type of electrode plate. Result of research indicate the time processing if using plate of copper electrode is during 30 minutes and using plate of aluminium electrode is during 20 minutes. Condition of strong current that used in process of electrochemical is only 0.8 ampere and concentration effective is 5.23 mg/l. The most effective type Al of electrode plate for reduction from waste and the efficiency of reduction is 98 %. (author)

  20. Optimizing the solar photo-Fenton process in the treatment of contaminated water. Determination of intrinsic kinetic constants for scale-up

    Energy Technology Data Exchange (ETDEWEB)

    Rodriguez, Miguel [Universidad de Los Andes, Escuela Basica de Ingenieria, La Hechicera, Merida (Venezuela); Malato, Sixto [Plataforma Solar de Almeria, Tabernas (PSA) (Spain); Pulgarin, Cesar [Institute of Environmental Engineering, Laboratory for Environmental Biotechnology, Swiss Federal Institute of Technology (EPFL), CH-1015 Lausanne (Switzerland); Contreras, Sandra; Curco, David; Gimenez, Jaime; Esplugas, Santiago [Department d' Enginyeria Quimica i Metallurgia, Universitat de Barcelona, Marti i Franques 1, 08028 Barcelona (Spain)

    2005-10-01

    The elimination of aromatic compounds present in surface water by photo-Fenton with sunlight as the source of radiation was studied. The concentrations of Fe{sup 3+} and H{sub 2}O{sub 2} are key factors for this process. A solar simulator and a prototype parabolic collector were used as laboratory-scale reactors to find the parameters of those key factors to be used in the CPC (compound parabolic collector) pilot plant reactor. The initial mineralization rate constant (k{sub obs}) was determined and evaluated at different Fe{sup 3+} and H{sub 2}O{sub 2} concentrations to find the best values for maximum efficiency. In all the experiments the mineralization of an aqueous phenol solution was described by assuming a pseudo-first-order reaction. The intrinsic kinetic constants not dependent on the lighting conditions were also estimated for scale-up. (author)

  1. Computer simulation of monolayer growth kinetics of Fe2B phase during the paste-boriding process: Influence of the paste thickness

    International Nuclear Information System (INIS)

    Keddam, M.

    2006-01-01

    This paper deals with the effect of boron paste thickness on the study of the monolayer growth kinetics of Fe 2 B phase forming on AISI 1045 steel by the paste-boriding process. A mathematical diffusion model based on the Fick's phenomenological equations was applied in order to estimate the growth rate constant at (Fe 2 B/γ-Fe) interface, the layer thickness of iron boride as well as the associated mass gain depending on the boriding parameters such as time, temperature and surface boron concentration related to the boron paste thickness. The simulation results are found to be in a fairly good agreement with the experimental data derived from the literature

  2. Kinetics of the processes, plasma parameters, and output characteristics of a UV emitter operating on XeI molecules and iodine molecules and atoms

    Energy Technology Data Exchange (ETDEWEB)

    Shuaibov, A. K.; Grabovaya, I. A.; Minya, A. I.; Homoki, Z. T. [Uzhgorod National University (Ukraine); Kalyuzhnaya, A. G.; Shchedrin, A. I. [National Academy of Sciences of Ukraine, Institute of Physics (Ukraine)

    2011-03-15

    A kinetic model of the processes occurring in the plasma of a high-power low-pressure gas-discharge lamp is presented, and the output characteristics of the lamp are described. The lamp is excited by a longitudinal glow discharge and emits the I{sub 2}(D Prime -A Prime ) 342-nm and XeI(B-X) 253-nm bands and the 206.2-nm spectral line of atomic iodine. When the emitter operates in a sealed-off mode on the p(He): p(Xe): p(I{sub 2}) = 400: 120: (100-200) Pa mixture, the fractions of the UV radiation power of iodine atoms, exciplex molecules of xenon iodide, and iodine molecules comprise 55, 10, and 35%, respectively. At the optimal partial pressure, the maximum total radiation power of the lamp reaches 37 W, the energy efficiency being about 15%.

  3. Adsorption analysis equilibria and kinetics

    CERN Document Server

    Do, Duong D

    1998-01-01

    This book covers topics of equilibria and kinetics of adsorption in porous media. Fundamental equilibria and kinetics are dealt with for homogeneous as well as heterogeneous particles. Five chapters of the book deal with equilibria and eight chapters deal with kinetics. Single component as well as multicomponent systems are discussed. In kinetics analysis, we deal with the various mass transport processes and their interactions inside a porous particle. Conventional approaches as well as the new approach using Maxwell-Stefan equations are presented. Various methods to measure diffusivity, such

  4. Quantum kinetic theory

    CERN Document Server

    Bonitz, Michael

    2016-01-01

    This book presents quantum kinetic theory in a comprehensive way. The focus is on density operator methods and on non-equilibrium Green functions. The theory allows to rigorously treat nonequilibrium dynamics in quantum many-body systems. Of particular interest are ultrafast processes in plasmas, condensed matter and trapped atoms that are stimulated by rapidly developing experiments with short pulse lasers and free electron lasers. To describe these experiments theoretically, the most powerful approach is given by non-Markovian quantum kinetic equations that are discussed in detail, including computational aspects.

  5. Morphology and Precipitation Kinetics of MnS in Low-Carbon Steel During Thin Slab Continuous Casting Process

    Institute of Scientific and Technical Information of China (English)

    YU Hao; KANG Yong-lin; ZHAO Zheng-zhi; SUN Hao

    2006-01-01

    The morphology of manganese sulfide formed during thin slab continuous casting process in low-carbon steel produced by compact strip production (CSP) technique was investigated. Using transmission electron microscopy analysis, it was seen that a majority of manganese sulfides precipitated at austenite grain boundaries, the morphologies of which were spherical or close to the spherical shape and the size of MnS precipitates ranged from 30 nm to 100 nm. A mathematical model of the manganese sulfide precipitation in this process was developed based on classical nucleation theory. Under the given conditions, the starting and finishing precipitation temperatures of MnS in the continuous casting thin slab of the studied low-carbon steel are 1 189 ℃ and 1 171 ℃, respectively, and the average diameter of MnS precipitates is about 48 nm within this precipitation temperature range. The influences of chemical components and thermo-mechanical processing conditions on the precipitation behavior of MnS in the same process were also discussed.

  6. Crystallite growth kinetics of TiO2 surface modification with 9 mol% ZnO prepared by a coprecipitation process

    International Nuclear Information System (INIS)

    Ko, Horng-Huey; Hsi, Chi-Shiung; Wang, Moo-Chin; Zhao, Xiujian

    2014-01-01

    Highlights: • TiO 2 powder surface modification with 9 mol% ZnO was obtained. • Phase transformation from anatase to rutile was hindered by ZnO added. • Growth kinetic of anatase TiO 2 nanocrystallites in T-9Z powders was described as: D A,9 2 =2.42×10 5 ×exp(-39.9×10 3 /RT). • Growth kinetic of rutile TiO 2 nanocrystallites in T-9Z powders was described as: D R,9 2 =8.49×10 5 ×exp(-47.6×10 3 /RT) rutile TiO 2 . -- Abstract: The nanocrystallite growth of TiO 2 surface modification with 9 mol% ZnO prepared by a coprecipitation process has been studied. Thermogravimetric and differential thermal analysis (TG/DTA), X-ray diffraction (XRD), transmission electron microscopy (TEM), selected area electron diffraction (SAED) and UV–VIS–NIR spectrophotometry have been utilized to characterize the TiO 2 nanocrystallites surface modification with 9 mol% ZnO (denoted by T-9Z). The DTA result shows that the anatase TiO 2 first formed at 533 K and the completion of anatase TiO 2 crystallization occurred at 745 K for the T-9Z freeze-dried precursor powders. XRD results reveal that the anatase and rutile TiO 2 coexist when the T-9Z freeze-dried precursor powders were calcined at 523–973 K for 2 h. When the T-9Z freeze-dried precursor powders were calcined at 973 K for 2 h, rutile TiO 2 was the major phase, and the minor phases were anatase TiO 2 and Zn 2 Ti 3 O 8 . The phase was composed of the rutile TiO 2 and Zn 2 TiO 4 for the T-9Z freeze-dried precursor powders after calcination at 1273 K for 2 h. The growth kinetics of TiO 2 nanocrystallites in T-9Z powders were described as: D A,9 2 =2.42×10 5 ×exp(-39.9×10 3 /RT)and D R,9 2 =8.49×10 5 ×exp(-47.6×10 3 /RT) for anatase and rutile TiO 2 nanocrystallites respectively. The analysis results of UV/VIS/NIR spectra reveal that the T-9Z freeze-dried precursor powders after calcination have a red-shifted effect with increasing calcination temperature and can be used as a UVA-attenuating agent

  7. THE KINETICS OF CONTAMINANTS ACCUMULATION IN THE JET FUEL DURING THE TECHNOLOGICAL PROCESS OF ITS PREPARATION FOR AIRCRAFT REFUELING

    OpenAIRE

    A. A. Brailko

    2017-01-01

    Much attention is payed to the tasks for ensuring domestic and international aircraft safety and regularity, which are multifaceted and complex. One of them is the system of ensuring the quality of aviation fuel for refueling aircraft at airports. A significant influence of the quality, chemical composition and fuel range on the reliability and lifetime of components and parts of the aircraft fuel system was studied in the process of development and experience accumulation of aircraft operati...

  8. Kinetics of non-equilibrium processes in non-linear crystals of lithium borates excited with synchrotron radiation

    CERN Document Server

    Ogorodnikov, I N; Isaenko, L I; Zinin, E I; Kruzhalov, A V

    2000-01-01

    The paper presents the results of a study of the LiB sub 3 O sub 5 and Li sub 2 B sub 4 O sub 7 crystals by the use of the luminescent spectroscopy with the sub-nanosecond time resolution under excitation of the high-power synchrotron radiation. The commonness in the origin of the non-equilibrium processes in these crystals as well as the observed differences in the luminescence manifestations is discussed.

  9. Kinetics of non-equilibrium processes in non-linear crystals of lithium borates excited with synchrotron radiation

    Energy Technology Data Exchange (ETDEWEB)

    Ogorodnikov, I.N. E-mail: ogo@dpt.ustu.ru; Pustovarov, V.A.; Isaenko, L.I.; Zinin, E.I.; Kruzhalov, A.V

    2000-06-21

    The paper presents the results of a study of the LiB{sub 3}O{sub 5} and Li{sub 2}B{sub 4}O{sub 7} crystals by the use of the luminescent spectroscopy with the sub-nanosecond time resolution under excitation of the high-power synchrotron radiation. The commonness in the origin of the non-equilibrium processes in these crystals as well as the observed differences in the luminescence manifestations is discussed.

  10. Fermentation of Saccharomyces cerevisiae - Combining kinetic modeling and optimization techniques points out avenues to effective process design.

    Science.gov (United States)

    Scheiblauer, Johannes; Scheiner, Stefan; Joksch, Martin; Kavsek, Barbara

    2018-09-14

    A combined experimental/theoretical approach is presented, for improving the predictability of Saccharomyces cerevisiae fermentations. In particular, a mathematical model was developed explicitly taking into account the main mechanisms of the fermentation process, allowing for continuous computation of key process variables, including the biomass concentration and the respiratory quotient (RQ). For model calibration and experimental validation, batch and fed-batch fermentations were carried out. Comparison of the model-predicted biomass concentrations and RQ developments with the corresponding experimentally recorded values shows a remarkably good agreement for both batch and fed-batch processes, confirming the adequacy of the model. Furthermore, sensitivity studies were performed, in order to identify model parameters whose variations have significant effects on the model predictions: our model responds with significant sensitivity to the variations of only six parameters. These studies provide a valuable basis for model reduction, as also demonstrated in this paper. Finally, optimization-based parametric studies demonstrate how our model can be utilized for improving the efficiency of Saccharomyces cerevisiae fermentations. Copyright © 2018 Elsevier Ltd. All rights reserved.

  11. Technospheric Mining of Rare Earth Elements from Bauxite Residue (Red Mud): Process Optimization, Kinetic Investigation, and Microwave Pretreatment.

    Science.gov (United States)

    Reid, Sable; Tam, Jason; Yang, Mingfan; Azimi, Gisele

    2017-11-10

    Some rare earth elements (REEs) are classified under critical materials, i.e., essential in use and subject to supply risk, due to their increasing demand, monopolistic supply, and environmentally unsustainable and expensive mining practices. To tackle the REE supply challenge, new initiatives have been started focusing on their extraction from alternative secondary resources. This study puts the emphasis on technospheric mining of REEs from bauxite residue (red mud) produced by the aluminum industry. Characterization results showed the bauxite residue sample contains about 0.03 wt% REEs. Systematic leaching experiments showed that concentrated HNO 3 is the most effective lixiviant. However, because of the process complexities, H 2 SO 4 was selected as the lixiviant. To further enhance the leaching efficiency, a novel process based on microwave pretreatment was employed. Results indicated that microwave pretreatment creates cracks and pores in the particles, enabling the lixiviant to diffuse further into the particles, bringing more REEs into solution, yielding of 64.2% and 78.7% for Sc and Nd, respectively, which are higher than the maximum obtained when HNO 3 was used. This novel process of "H 2 SO 4 leaching-coupled with-microwave pretreatment" proves to be a promising technique that can help realize the technological potential of REE recovery from secondary resources, particularly bauxite residue.

  12. Developing a Steady-state Kinetic Model for Industrial Scale Semi-Regenerative Catalytic Naphtha Reforming Process

    Directory of Open Access Journals (Sweden)

    Seif Mohaddecy, R.

    2014-05-01

    Full Text Available Due to the demand for high octane gasoline as a transportation fuel, the catalytic naphtha reformer has become one of the most important processes in petroleum refineries. In this research, the steady-state modelling of a catalytic fixed-bed naphtha reforming process to predict the momentous output variables was studied. These variables were octane number, yield, hydrogen purity, and temperature of all reforming reactors. To do such a task, an industrial scale semi-regenerative catalytic naphtha reforming unit was studied and modelled. In addition, to evaluate the developed model, the predicted variables i.e. outlet temperatures of reactors, research octane number, yield of gasoline and hydrogen purity were compared against actual data. The results showed that there is a close mapping between the actual and predicted variables, and the mean relative absolute deviation of the mentioned process variables were 0.38 %, 0.52 %, 0.54 %, 0.32 %, 4.8 % and 3.2 %, respectively.

  13. Sorption isotherms, kinetic and optimization process of amino acid proline based polymer nanocomposite for the removal of selected textile dyes from industrial wastewater.

    Science.gov (United States)

    Raghunath, Sharista; Anand, K; Gengan, R M; Nayunigari, Mithil Kumar; Maity, Arjun

    2016-12-01

    In this article, adsorption and kinetic studies were carried out on three textile dyes, namely Reactive Blue 222 (RB 222), Reactive Red 195 (RR 195) and Reactive Yellow 145 (RY 145). The dyes studied in a mixture were adsorbed under various conditions onto PRO-BEN, a bentonite modified with a new cationic proline polymer (l-proline-epichlorohydrin polymer). The proline polymer was characterized by 1 H NMR, Fourier transform infrared spectroscopy (FT-IR), dynamic light scattering (DLS) and TEM. The PRO-BEN composite was characterized by FT-IR, dynamic light scattering (DLS) (zeta potential), TEM imaging, SEM/EDX and X-ray photoelectron spectroscopy (characterize the binding energy). During adsorption studies, factors involving pH, temperature, the initial concentrations of the dyes and the quantity of PRO-BEN used during adsorption were established. The results revealed that the adsorption mechanism was categorized by the Langmuir type 1 isotherm. The adsorption data followed the pseudo-second order kinetic model. The intraparticle diffusion model indicated that adsorption did not only depend on the intraparticle diffusion of the dyes. The thermodynamic parameters verified that the adsorption process was spontaneous and exothermic. The Gibbs free energy values indicated that physisorption had occurred. Successful adsorption of dyes from an industrial effluent was achieved. Desorption studies concluded that PRO-BEN desorbed the dyes better than alumina. This can thereby be viewed as a recyclable remediation material. The PRO-BEN composite could be a cost efficient alternative towards the removal of organic dyes in wastewater treatment. Copyright © 2016 Elsevier B.V. All rights reserved.

  14. APEX (Aqueous Photochemistry of Environmentally occurring Xenobiotics): a free software tool to predict the kinetics of photochemical processes in surface waters.

    Science.gov (United States)

    Bodrato, Marco; Vione, Davide

    2014-04-01

    The APEX software predicts the photochemical transformation kinetics of xenobiotics in surface waters as a function of: photoreactivity parameters (direct photolysis quantum yield and second-order reaction rate constants with transient species, namely ˙OH, CO₃(-)˙, (1)O₂ and the triplet states of chromophoric dissolved organic matter, (3)CDOM*), water chemistry (nitrate, nitrite, bicarbonate, carbonate, bromide and dissolved organic carbon, DOC), and water depth (more specifically, the optical path length of sunlight in water). It applies to well-mixed surface water layers, including the epilimnion of stratified lakes, and the output data are average values over the considered water column. Based on intermediate formation yields from the parent compound via the different photochemical pathways, the software can also predict intermediate formation kinetics and overall yield. APEX is based on a photochemical model that has been validated against available field data of pollutant phototransformation, with good agreement between model predictions and field results. The APEX software makes allowance for different levels of knowledge of a photochemical system. For instance, the absorption spectrum of surface water can be used if known, or otherwise it can be modelled from the values of DOC. Also the direct photolysis quantum yield can be entered as a detailed wavelength trend, as a single value (constant or average), or it can be defined as a variable if unknown. APEX is based on the free software Octave. Additional applications are provided within APEX to assess the σ-level uncertainty of the results and the seasonal trend of photochemical processes.

  15. Effect of Process Variables, Adsorption Kinetics and Equilibrium Studies of Hexavalent Chromium Removal from Aqueous Solution by Date Seeds and its Activated Carbon by ZnCl2

    Directory of Open Access Journals (Sweden)

    Samar K. Theydan

    2018-03-01

    Full Text Available The adsorption of hexavalent chromium by preparing activated carbon from date seeds with zinc chloride as chemical activator and granular date seeds was studied in a batch system. The characteristics of date seeds and prepared activated carbon (ZAC were determined and found to have a surface area 500.01 m2/g and 1050.01 m2/g , respectively and iodine number of 485.78 mg/g and 1012.91 mg/g, respectively. The effects of PH value (2-12, initial sorbate concentration(50-450mg/L, adsorbent weight (0.004-0.036g and contact time (30-150 min on the adsorption process were studied . For Cr(VI adsorption on ZAC, at 120 min time contact, pH solution 2 and 0.02 adsorbent weight will achieve an amount of 35.6 mg/g adsorbed . While when use date seeds as adsorbent , conditions of 3 solution pH, 0.02 absorbent weight , and 120 contact time gave 26.49 mg/g adsorbed amount. Using both Langmuir, Freundlich and Sips models were explain the dsorption isotherms. It declare that the Sips model fits well with the experimental data with a maximum Cr( VI adsorption capacity for (ZAC and granular date stone 233.493 and 208.055 mg/g, respectively . The kinetics data which obtained at different initial Cr(VI concentrations were examined by using pseudo-first-order, pseudo-second-order, and intra-particle diffusion models . The result gained showed that the second-order model was only describing well the empirical kinetics data of both (ZAC and granular date seeds. It was noticed that the granular date seeds has adsorption performance lower than the (ZAC.

  16. Empirical model based on Weibull distribution describing the destruction kinetics of natural microbiota in pineapple (Ananas comosus L.) puree during high-pressure processing.

    Science.gov (United States)

    Chakraborty, Snehasis; Rao, Pavuluri Srinivasa; Mishra, Hari Niwas

    2015-10-15

    High pressure inactivation of natural microbiota viz. aerobic mesophiles (AM), psychrotrophs (PC), yeasts and molds (YM), total coliforms (TC) and lactic acid bacteria (LAB) in pineapple puree was studied within the experimental domain of 0.1-600 MPa and 30-50 °C with a treatment time up to 20 min. A complete destruction of yeasts and molds was obtained at 500 MPa/50 °C/15 min; whereas no counts were detected for TC and LAB at 300 MPa/30 °C/15 min. A maximum of two log cycle reductions was obtained for YM during pulse pressurization at the severe process intensity of 600 MPa/50 °C/20 min. The Weibull model clearly described the non-linearity of the survival curves during the isobaric period. The tailing effect, as confirmed by the shape parameter (β) of the survival curve, was obtained in case of YM (β1) was observed for the other microbial groups. Analogous to thermal death kinetics, the activation energy (Ea, kJ·mol(-1)) and the activation volume (Va, mL·mol(-1)) values were computed further to describe the temperature and pressure dependencies of the scale parameter (δ, min), respectively. A higher δ value was obtained for each microbe at a lower temperature and it decreased with an increase in pressure. A secondary kinetic model was developed describing the inactivation rate (k, min(-1)) as a function of pressure (P, MPa) and temperature (T, K) including the dependencies of Ea and Va on P and T, respectively. Copyright © 2015 Elsevier B.V. All rights reserved.

  17. The effect of cation:anion ratio in solution on the mechanism of barite growth at constant supersaturation: Role of the desolvation process on the growth kinetics

    Science.gov (United States)

    Kowacz, M.; Putnis, C. V.; Putnis, A.

    2007-11-01

    The mechanism of barite growth has been investigated in a fluid cell of an Atomic Force Microscope by passing solutions of constant supersaturation ( Ω) but variable ion activity ratio ( r=a/a) over a barite substrate.The observed dependence of step-spreading velocity on solution stoichiometry can be explained by considering non-equivalent attachment frequency factors for the cation and anion. We show that the potential for two-dimensional nucleation changes under a constant thermodynamic driving force due to the kinetics of barium integration into the surface, and that the growth mode changes from preexisting step advancement to island spreading as the cation/anion activity ratio increases. Scanning electron microscopy studies of crystals grown in bulk solutions support our findings that matching the ion ratio in the fluid to that of the crystal lattice does not result in maximum growth and nucleation rates. Significantly more rapid rates correspond to solution stoichiometries where [Ba 2+] is in excess with respect to [ SO42-]. Experiments performed in dilute aqueous solutions of methanol show that even 0.02 molar fraction of organic cosolvent in the growth solution significantly accelerates step growth velocity and nucleation rates (while keeping Ω the same as in the reference solution in water). Our observations suggest that the effect of methanol on barite growth results first of all from reduction of the barrier that prevents the Ba 2+ from reaching the surface and corroborate the hypothesis that desolvation of the cation and of the surface is the rate limiting kinetic process for two-dimensional nucleation and for crystal growth.

  18. Metabolic and process engineering for biodesulfurization in Gram-negative bacteria.

    Science.gov (United States)

    Martínez, I; El-Said Mohamed, M; Santos, V E; García, J L; García-Ochoa, F; Díaz, E

    2017-11-20

    Microbial desulfurization or biodesulfurization (BDS) is an attractive low-cost and environmentally friendly complementary technology to the hydrotreating chemical process based on the potential of certain bacteria to specifically remove sulfur from S-heterocyclic compounds of crude fuels that are recalcitrant to the chemical treatments. The 4S or Dsz sulfur specific pathway for dibenzothiophene (DBT) and alkyl-substituted DBTs, widely used as model S-heterocyclic compounds, has been extensively studied at the physiological, biochemical and genetic levels mainly in Gram-positive bacteria. Nevertheless, several Gram-negative bacteria have been also used in BDS because they are endowed with some properties, e.g., broad metabolic versatility and easy genetic and genomic manipulation, that make them suitable chassis for systems metabolic engineering strategies. A high number of recombinant bacteria, many of which are Pseudomonas strains, have been constructed to overcome the major bottlenecks of the desulfurization process, i.e., expression of the dsz operon, activity of the Dsz enzymes, retro-inhibition of the Dsz pathway, availability of reducing power, uptake-secretion of substrate and intermediates, tolerance to organic solvents and metals, and other host-specific limitations. However, to attain a BDS process with industrial applicability, it is necessary to apply all the knowledge and advances achieved at the genetic and metabolic levels to the process engineering level, i.e., kinetic modelling, scale-up of biphasic systems, enhancing mass transfer rates, biocatalyst separation, etc. The production of high-added value products derived from the organosulfur material present in oil can be regarded also as an economically viable process that has barely begun to be explored. Copyright © 2017 Elsevier B.V. All rights reserved.

  19. THE KINETICS OF CONTAMINANTS ACCUMULATION IN THE JET FUEL DURING THE TECHNOLOGICAL PROCESS OF ITS PREPARATION FOR AIRCRAFT REFUELING

    Directory of Open Access Journals (Sweden)

    A. A. Brailko

    2017-01-01

    Full Text Available Much attention is payed to the tasks for ensuring domestic and international aircraft safety and regularity, which are multifaceted and complex. One of them is the system of ensuring the quality of aviation fuel for refueling aircraft at airports. A significant influence of the quality, chemical composition and fuel range on the reliability and lifetime of components and parts of the aircraft fuel system was studied in the process of development and experience accumulation of aircraft operating, processes of aviation fuel production, as well as during storage, quality control, transportation, refueling preparation and aircraft refueling. Currently, work is being done to study the influence of fuel quality on the units of the technological scheme of fuel-filling complexes, which provide the required cleanliness of the fuel according to the regulations. The article describes the trend level of aviation fuel cleanliness at the stages from receipt to issuance to the refueling station. The evaluation of compliance with existing regulations on the level of jet fuel cleanliness and the efficiency of fuel cleaning facilities is carried out. It is stated that one of the problems of insufficient level of aviation fuel cleaning quality is a violation of the acceptable contamination level of the fuel before the filter. It was found that the disadvantage of the used filter paper is the fiber wash out process. According to this research it was found that while cleaning fuel from mechanical admixtures it is necessary to take into account the technical condition of the filtering element, and proposal was developed for fuel-filling systems to ensure aviation fuel cleanliness in compliance with regulations.

  20. Kinetics of Acid Orange 7 oxidation by using carbon fiber and reticulated vitreous carbon in an electro-Fenton process.

    Science.gov (United States)

    Ramírez-Pereda, Blenda; Álvarez-Gallegos, Alberto; Rangel-Peraza, Jesús Gabriel; Bustos-Terrones, Yaneth A

    2018-05-01

    In this study, a micro-scale parallel plate reactor was built to electrochemically generate hydrogen peroxide (H 2 O 2 ) and to develop the Fenton reaction in situ, for the treatment of toxic organic pollutants. Two types of carbon materials were compared and used as cathodes: unidirectional carbon fiber (CF) and reticulated vitreous carbon (RVC). As anode, a stainless steel mesh was used. The results of H 2 O 2 were experimentally compared by means of electrogeneration process. RVC cathode with dimensions of 2.5 × 1 × 5 cm (170 mA and variable voltage V = 2.0-2.7) and 180 min produced 5.3 mM H 2 O 2 , with an H 2 O 2 production efficiency of 54%. Unidirectional carbon fiber cathode produced 7.5 mM of H 2 O 2 (96% of H 2 O 2 production efficiency) when a voltage of 1.8 V was applied during 180 min to a total area of 480 cm 2 of this material. Acid Orange 7 (AO7) was degraded to a concentration of 0.16 mM during the first 40 min of the process, which represented 95% of the initial concentration. Electrolysis process removed nearly 100% of the AO7 using both cathodes at the end of these experiments (180 min). Copyright © 2018 Elsevier Ltd. All rights reserved.

  1. Physisorption kinetics

    CERN Document Server

    Kreuzer, Hans Jürgen

    1986-01-01

    This monograph deals with the kinetics of adsorption and desorption of molecules physisorbed on solid surfaces. Although frequent and detailed reference is made to experiment, it is mainly concerned with the theory of the subject. In this, we have attempted to present a unified picture based on the master equation approach. Physisorption kinetics is by no means a closed and mature subject; rather, in writing this monograph we intended to survey a field very much in flux, to assess its achievements so far, and to give a reasonable basis from which further developments can take off. For this reason we have included many papers in the bibliography that are not referred to in the text but are of relevance to physisorption. To keep this monograph to a reasonable size, and also to allow for some unity in the presentation of the material, we had to omit a number of topics related to physisorption kinetics. We have not covered to any extent the equilibrium properties of physisorbed layers such as structures, phase tr...

  2. Probing into the effects of a magnetic field on the electrode processes of iron in sulphuric acid solutions with dichromate based on the fundamental electrochemistry kinetics

    International Nuclear Information System (INIS)

    Lu Zhanpeng; Huang Delun; Yang Wu

    2005-01-01

    kinetics after introducing a coefficient term of the magnetic field effect on the mass transfer process of reactive ions

  3. Optimization of the immobilization process of β-galatosidade by combined entrapment-cross-linking and the kinetics of lactose hydrolysis

    Directory of Open Access Journals (Sweden)

    F. F. Freitas

    2012-03-01

    Full Text Available The immobilization of Aspergillus oryzae β-galactosidase was achieved by entrapment in sodium alginate and gelatin and cross-linking with glutaraldehyde. The optimal concentrations of the aforementioned variables in the immobilization process were determined using an orthogonal central composite design with an orthogonal axial value of 1.35313. The concentrations of alginate, gelatin and glutaraldehyde that provided the greatest enzymatic activity were 6.60%, 4.05% and 3.64% (w/v, respectively. The stability of the immobilized enzyme under the optimal conditions was evaluated through daily activity assays. After 25 uses, a 20% decrease in the enzymatic activity was observed, indicating that the immobilization process could be used to produce a stable biocatalyst. This study investigates the influence of lactose and product concentrations on kinetic reaction hydrolysis. The concentration ranges for the studied variables were 10 to 56 g/L for lactose and 0 to 11.5 g/L for glucose and galactose. Only galactose presented a competitive inhibitory effect.

  4. Kinetic Analysis of Isothermal Decomposition Process of Sodium Bicarbonate Using the Weibull Probability Function—Estimation of Density Distribution Functions of the Apparent Activation Energies

    Science.gov (United States)

    Janković, Bojan

    2009-10-01

    The decomposition process of sodium bicarbonate (NaHCO3) has been studied by thermogravimetry in isothermal conditions at four different operating temperatures (380 K, 400 K, 420 K, and 440 K). It was found that the experimental integral and differential conversion curves at the different operating temperatures can be successfully described by the isothermal Weibull distribution function with a unique value of the shape parameter ( β = 1.07). It was also established that the Weibull distribution parameters ( β and η) show independent behavior on the operating temperature. Using the integral and differential (Friedman) isoconversional methods, in the conversion (α) range of 0.20 ≤ α ≤ 0.80, the apparent activation energy ( E a ) value was approximately constant ( E a, int = 95.2 kJmol-1 and E a, diff = 96.6 kJmol-1, respectively). The values of E a calculated by both isoconversional methods are in good agreement with the value of E a evaluated from the Arrhenius equation (94.3 kJmol-1), which was expressed through the scale distribution parameter ( η). The Málek isothermal procedure was used for estimation of the kinetic model for the investigated decomposition process. It was found that the two-parameter Šesták-Berggren (SB) autocatalytic model best describes the NaHCO3 decomposition process with the conversion function f(α) = α0.18(1-α)1.19. It was also concluded that the calculated density distribution functions of the apparent activation energies ( ddfE a ’s) are not dependent on the operating temperature, which exhibit the highly symmetrical behavior (shape factor = 1.00). The obtained isothermal decomposition results were compared with corresponding results of the nonisothermal decomposition process of NaHCO3.

  5. UV-lysogenic induction of lambda phage in lexAl mutants of Escherichia coli: kinetics of the process

    Energy Technology Data Exchange (ETDEWEB)

    Carvalho, R.E.S.; Leitao, A.C. (Rio de Janeiro Univ. (Brazil). Inst. de Biofisica)

    1984-05-01

    Although the lex gene has been described as being required for lysogenic induction, both this work and the work of others have reported lambda prophage induction in some lexA mutants. However, the characteristics of the process were not defined. UV induction of prophage in a lexAl mutant is described at a slightly lower level and requiring 2 times longer than the wild type. As demonstrated in some work, in cells treated with low levels of rifampicin (RIF) no new synthesis of RecA protein is needed for the prophage induction although the onset of lysis is delayed. It is suggested that the lysogenic induction in lexA cells is due to the same mechanism that induces prophage in the wild type cells treated with RIF. That is, the induction is due to the cleavage of lambda repressor by the basal RecA protease in the DNA-single-strand gap, since RecA protease and monomer repressor both have high affinity for this type of DNA. So, LexA protein need not be cleaved for the prophage induction. No Weigle-reactivation (WR) was detected in the lex mutant even after a long post-irradiation incubation, suggesting that unlike prophage induction, WR requires LexA protein cleavage.

  6. Production of poly(malic acid) from sugarcane juice in fermentation by Aureobasidium pullulans: Kinetics and process economics.

    Science.gov (United States)

    Wei, Peilian; Cheng, Chi; Lin, Meng; Zhou, Yipin; Yang, Shang-Tian

    2017-01-01

    Poly(β-l-malic acid) (PMA) is a biodegradable polymer with many potential biomedical applications. PMA can be readily hydrolyzed to malic acid (MA), which is widely used as an acidulant in foods and pharmaceuticals. PMA production from sucrose and sugarcane juice by Aureobasidium pullulans ZX-10 was studied in shake-flasks and bioreactors, confirming that sugarcane juice can be used as an economical substrate without any pretreatment or nutrients supplementation. A high PMA titer of 116.3g/L and yield of 0.41g/g were achieved in fed-batch fermentation. A high productivity of 0.66g/L·h was achieved in repeated-batch fermentation with cell recycle. These results compared favorably with those obtained from glucose and other biomass feedstocks. A process economic analysis showed that PMA could be produced from sugarcane juice at a cost of $1.33/kg, offering a cost-competitive bio-based PMA for industrial applications. Copyright © 2016 Elsevier Ltd. All rights reserved.

  7. Self-assembly of the yeast actomyosin contractile ring as an aggregation process: kinetics of formation and instability regimes

    Science.gov (United States)

    Ojkic, Nikola; Vavylonis, Dimitrios

    2009-03-01

    Fission yeast cells assemble an equatorial contractile ring for cytokinesis, the last step of mitosis. The ring assembles from ˜ 65 membrane-bound ``nodes''' containing myosin motors and other proteins. Actin filaments that grow out from the nodes establish transient connections among the nodes and aid in pulling them together in a process that appears as pair-wise attraction (Vavylonis et al. Science 97:319, 2008). We used scaling arguments, coarse grained stability analysis of homogeneous states, and Monte Carlo simulations of simple models, to explore the conditions that yield fast and efficient ring formation, as opposed to formation of isolated clumps. We described our results as a function of: number of nodes, rate of establishing connections, range of node interaction, distance traveled per node interaction and broad band width, w. Uniform cortical 2d distributions of nodes are stable over short times due to randomness of connections among nodes, but become unstable over long times due to fluctuations in the initial node distribution. Successful condensation of nodes into a ring requires sufficiently small w such that lateral contraction occurs faster then clump formation.

  8. KINETIC MODELS STUDY OF HYDRODESULPHURIZATION VACUUM DISTILLATE REACTION

    Directory of Open Access Journals (Sweden)

    AbdulMunem A. Karim

    2013-05-01

    Full Text Available    This study deals with  kinetics of hydrodesulphurization (HDS reaction of vacuum gas oil (611-833 K which was distillated from Kirkuk crude oil and which was obtained by blending the fractions, light vacuum gas oil (611 - 650 K, medium vacuum gas oil (650-690 K, heavy vacuum gas oil (690-727 K and very heavy vacuum gas oil (727-833 K.   The vacuum gas oil was hydrotreated on a commercial cobalt-molybdenum alumina catalyst presulfied at specified conditions in a laboratory trickle bed reactor. The reaction temperature range (583-643 K,liquid hourly space velocity range (1.5-3.75 h-1 and hydrogen pressure was kept constant at 3.5 MPa with hydrogen to oil ratio about 250 lt/lt.           The conversion results for desulphurization reaction appeared to obey the second order reaction. According to this model, the rate constants for desulphurization reaction were determined. Finally, the apparent activation energy (Ea, enthalpy of activation ( H* and entropy ( S* were calculated based on the values of rate constant (k2 and were equal 80.3792 KJ/mole, 75.2974 KJ/mole and 197.493 J/mole, respectively.

  9. Hydrothermal liquefaction oil and hydrotreated product from pine feedstock characterized by heteronuclear two-dimensional NMR spectroscopy and FT-ICR mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Sudasinghe, Nilusha; Cort, John R.; Hallen, Richard T.; Olarte, Mariefel V.; Schmidt, Andrew J.; Schaub, Tanner

    2014-12-01

    Hydrothermal liquefaction (HTL) crude oil and hydrotreated product from pine tree farm waste (forest product residual, FPR) have been analyzed by direct infusion electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI FT-ICR MS) in both positive- and negative-ionization modes and high-resolution twodimensional heteronuclear 1H-13C NMR spectroscopy. FT-ICR MS resolves thousands of compounds in complex oils and provides unparalleled compositional details for individual molecules for identification of compound class (heteroatom content), type (number of rings plus double bonds to carbon or double bond equivalents (DBE) and carbon number (degree of alkylation). Heteronuclear 1H-13C NMR spectroscopy provides one-bond and multiple-bond correlations between pairs of 1H and 13C chemical shifts that are characteristic of different organic functional groups. Taken together this information provides a picture of the chemical composition of these oils. Pyrolysis crude oil product from pine wood was characterized for comparison. Generally, pyrolysis oil is comprised of a more diverse distribution of heteroatom classes with higher oxygen number relative to HTL oil as shown by both positive- and negative-ion ESI FT-ICR MS. A total of 300 N1, 594 O1 and 267 O2 compounds were observed as products of hydrotreatment. The relative abundance of N1O1, N1O2, N1O3, N2, N2O1, N2O2 and O3 compounds are reduced to different degrees after hydrotreatment and other higher heteroatom containing species (O4-O10, N1O4, N1O5 and N2O3) are completely removed by hydrotreatment.

  10. Tuning the nano/micro-structure and properties of melt-processed ternary composites of polypropylene/ethylene vinyl acetate blend and nanoclay: The influence of kinetic and thermodynamic parameters

    CSIR Research Space (South Africa)

    Mofokeng, Tladi G

    2017-09-01

    Full Text Available The present study reports the dependence of the nano/micro-structure and properties of polypropylene (PP)/ethylene vinyl acetate (EVA)/nanoclay ternary composites on the kinetics and thermodynamics of the melt-mixing process. The size of dispersed...

  11. Inappropriate Use of the Quasi-Reversible Electrode Kinetic Model in Simulation-Experiment Comparisons of Voltammetric Processes That Approach the Reversible Limit

    KAUST Repository

    Simonov, Alexandr N.; Morris, Graham P.; Mashkina, Elena A.; Bethwaite, Blair; Gillow, Kathryn; Baker, Ruth E.; Gavaghan, David J.; Bond, Alan M.

    2014-01-01

    Many electrode processes that approach the "reversible" (infinitely fast) limit under voltammetric conditions have been inappropriately analyzed by comparison of experimental data and theory derived from the "quasi-reversible" model. Simulations based on "reversible" and "quasi-reversible" models have been fitted to an extensive series of a.c. voltammetric experiments undertaken at macrodisk glassy carbon (GC) electrodes for oxidation of ferrocene (Fc0/+) in CH3CN (0.10 M (n-Bu)4NPF6) and reduction of [Ru(NH 3)6]3+ and [Fe(CN)6]3- in 1 M KCl aqueous electrolyte. The confidence with which parameters such as standard formal potential (E0), heterogeneous electron transfer rate constant at E0 (k0), charge transfer coefficient (α), uncompensated resistance (Ru), and double layer capacitance (CDL) can be reported using the "quasi- reversible" model has been assessed using bootstrapping and parameter sweep (contour plot) techniques. Underparameterization, such as that which occurs when modeling CDL with a potential independent value, results in a less than optimal level of experiment-theory agreement. Overparameterization may improve the agreement but easily results in generation of physically meaningful but incorrect values of the recovered parameters, as is the case with the very fast Fc0/+ and [Ru(NH3)6]3+/2+ processes. In summary, for fast electrode kinetics approaching the "reversible" limit, it is recommended that the "reversible" model be used for theory-experiment comparisons with only E0, R u, and CDL being quantified and a lower limit of k 0 being reported; e.g., k0 ≥ 9 cm s-1 for the Fc0/+ process. © 2014 American Chemical Society.

  12. Inappropriate Use of the Quasi-Reversible Electrode Kinetic Model in Simulation-Experiment Comparisons of Voltammetric Processes That Approach the Reversible Limit

    KAUST Repository

    Simonov, Alexandr N.

    2014-08-19

    Many electrode processes that approach the "reversible" (infinitely fast) limit under voltammetric conditions have been inappropriately analyzed by comparison of experimental data and theory derived from the "quasi-reversible" model. Simulations based on "reversible" and "quasi-reversible" models have been fitted to an extensive series of a.c. voltammetric experiments undertaken at macrodisk glassy carbon (GC) electrodes for oxidation of ferrocene (Fc0/+) in CH3CN (0.10 M (n-Bu)4NPF6) and reduction of [Ru(NH 3)6]3+ and [Fe(CN)6]3- in 1 M KCl aqueous electrolyte. The confidence with which parameters such as standard formal potential (E0), heterogeneous electron transfer rate constant at E0 (k0), charge transfer coefficient (α), uncompensated resistance (Ru), and double layer capacitance (CDL) can be reported using the "quasi- reversible" model has been assessed using bootstrapping and parameter sweep (contour plot) techniques. Underparameterization, such as that which occurs when modeling CDL with a potential independent value, results in a less than optimal level of experiment-theory agreement. Overparameterization may improve the agreement but easily results in generation of physically meaningful but incorrect values of the recovered parameters, as is the case with the very fast Fc0/+ and [Ru(NH3)6]3+/2+ processes. In summary, for fast electrode kinetics approaching the "reversible" limit, it is recommended that the "reversible" model be used for theory-experiment comparisons with only E0, R u, and CDL being quantified and a lower limit of k 0 being reported; e.g., k0 ≥ 9 cm s-1 for the Fc0/+ process. © 2014 American Chemical Society.

  13. Inappropriate use of the quasi-reversible electrode kinetic model in simulation-experiment comparisons of voltammetric processes that approach the reversible limit.

    Science.gov (United States)

    Simonov, Alexandr N; Morris, Graham P; Mashkina, Elena A; Bethwaite, Blair; Gillow, Kathryn; Baker, Ruth E; Gavaghan, David J; Bond, Alan M

    2014-08-19

    Many electrode processes that approach the "reversible" (infinitely fast) limit under voltammetric conditions have been inappropriately analyzed by comparison of experimental data and theory derived from the "quasi-reversible" model. Simulations based on "reversible" and "quasi-reversible" models have been fitted to an extensive series of a.c. voltammetric experiments undertaken at macrodisk glassy carbon (GC) electrodes for oxidation of ferrocene (Fc(0/+)) in CH3CN (0.10 M (n-Bu)4NPF6) and reduction of [Ru(NH3)6](3+) and [Fe(CN)6](3-) in 1 M KCl aqueous electrolyte. The confidence with which parameters such as standard formal potential (E(0)), heterogeneous electron transfer rate constant at E(0) (k(0)), charge transfer coefficient (α), uncompensated resistance (Ru), and double layer capacitance (CDL) can be reported using the "quasi-reversible" model has been assessed using bootstrapping and parameter sweep (contour plot) techniques. Underparameterization, such as that which occurs when modeling CDL with a potential independent value, results in a less than optimal level of experiment-theory agreement. Overparameterization may improve the agreement but easily results in generation of physically meaningful but incorrect values of the recovered parameters, as is the case with the very fast Fc(0/+) and [Ru(NH3)6](3+/2+) processes. In summary, for fast electrode kinetics approaching the "reversible" limit, it is recommended that the "reversible" model be used for theory-experiment comparisons with only E(0), Ru, and CDL being quantified and a lower limit of k(0) being reported; e.g., k(0) ≥ 9 cm s(-1) for the Fc(0/+) process.

  14. Tolrestat kinetics

    International Nuclear Information System (INIS)

    Hicks, D.R.; Kraml, M.; Cayen, M.N.; Dubuc, J.; Ryder, S.; Dvornik, D.

    1984-01-01

    The kinetics of tolrestat, a potent inhibitor of aldose reductase, were examined. Serum concentrations of tolrestat and of total 14 C were measured after dosing normal subjects and subjects with diabetes with 14 C-labeled tolrestat. In normal subjects, tolrestat was rapidly absorbed and disappearance from serum was biphasic. Distribution and elimination t 1/2s were approximately 2 and 10 to 12 hr, respectively, after single and multiple doses. Unchanged tolrestat accounted for the major portion of 14 C in serum. Radioactivity was rapidly and completely excreted in urine and feces in an approximate ratio of 2:1. Findings were much the same in subjects with diabetes. In normal subjects, the kinetics of oral tolrestat were independent of dose in the 10 to 800 mg range. Repetitive dosing did not result in unexpected cumulation. Tolrestat was more than 99% bound to serum protein; it did not compete with warfarin for binding sites but was displaced to some extent by high concentrations of tolbutamide or salicylate

  15. The Kinetics of Joined Action of Triplet-Triplet Annihilation and First-Order Decay of Molecules in T1 State in the Case of Nondominant First-Order Process: The Kinetic Model in the Case of Spatially Periodic Excitation

    Directory of Open Access Journals (Sweden)

    Paweł Borowicz

    2013-01-01

    Full Text Available In this paper the model developed for estimation of the diffusion coefficient of the molecules in the triplet state is presented. The model is based on the intuitive modification of the Smoluchowski equation for the time-dependent rate parameter. Since the sample is irradiated with the spatially periodic pattern nonexponential effects can be expected in the areas of the constructive interference of the exciting laser beams. This nonexponential effects introduce changes in the observed kinetics of the diffusion-controlled triplet-triplet annihilation. Due to irradiation with so-called long excitation pulse these non-exponential effects are very weak, so they can be described with introducing very simple correction to the kinetic model described in the first paper of this series. The values of diffusion coefficient of anthracene are used to calculate the annihilation radius from the data for spatially homogeneous excitation.

  16. Two-Step Production of Phenylpyruvic Acid from L-Phenylalanine by Growing and Resting Cells of Engineered Escherichia coli: Process Optimization and Kinetics Modeling.

    Directory of Open Access Journals (Sweden)

    Ying Hou

    Full Text Available Phenylpyruvic acid (PPA is widely used in the pharmaceutical, food, and chemical industries. Here, a two-step bioconversion process, involving growing and resting cells, was established to produce PPA from l-phenylalanine using the engineered Escherichia coli constructed previously. First, the biotransformation conditions for growing cells were optimized (l-phenylalanine concentration 20.0 g·L-1, temperature 35°C and a two-stage temperature control strategy (keep 20°C for 12 h and increase the temperature to 35°C until the end of biotransformation was performed. The biotransformation conditions for resting cells were then optimized in 3-L bioreactor and the optimized conditions were as follows: agitation speed 500 rpm, aeration rate 1.5 vvm, and l-phenylalanine concentration 30 g·L-1. The total maximal production (mass conversion rate reached 29.8 ± 2.1 g·L-1 (99.3% and 75.1 ± 2.5 g·L-1 (93.9% in the flask and 3-L bioreactor, respectively. Finally, a kinetic model was established, and it was revealed that the substrate and product inhibition were the main limiting factors for resting cell biotransformation.

  17. Two-Step Production of Phenylpyruvic Acid from L-Phenylalanine by Growing and Resting Cells of Engineered Escherichia coli: Process Optimization and Kinetics Modeling.

    Science.gov (United States)

    Hou, Ying; Hossain, Gazi Sakir; Li, Jianghua; Shin, Hyun-Dong; Liu, Long; Du, Guocheng; Chen, Jian

    2016-01-01

    Phenylpyruvic acid (PPA) is widely used in the pharmaceutical, food, and chemical industries. Here, a two-step bioconversion process, involving growing and resting cells, was established to produce PPA from l-phenylalanine using the engineered Escherichia coli constructed previously. First, the biotransformation conditions for growing cells were optimized (l-phenylalanine concentration 20.0 g·L-1, temperature 35°C) and a two-stage temperature control strategy (keep 20°C for 12 h and increase the temperature to 35°C until the end of biotransformation) was performed. The biotransformation conditions for resting cells were then optimized in 3-L bioreactor and the optimized conditions were as follows: agitation speed 500 rpm, aeration rate 1.5 vvm, and l-phenylalanine concentration 30 g·L-1. The total maximal production (mass conversion rate) reached 29.8 ± 2.1 g·L-1 (99.3%) and 75.1 ± 2.5 g·L-1 (93.9%) in the flask and 3-L bioreactor, respectively. Finally, a kinetic model was established, and it was revealed that the substrate and product inhibition were the main limiting factors for resting cell biotransformation.

  18. Decolorization of malachite green, decolorization kinetics and stoichiometry of ozone-malachite green and removal of antibacterial activity with ozonation processes

    Energy Technology Data Exchange (ETDEWEB)

    Kusvuran, Erdal, E-mail: erdalkusvuran@yahoo.com [Chemistry Department, Arts and Sciences Faculty, Cukurova University, 01330 Balcali, Adana (Turkey); Gulnaz, Osman [Biology Department, Arts and Sciences Faculty, Cukurova University, 01330 Balcali, Adana (Turkey); Samil, Ali [Chemistry Department, Arts and Sciences Faculty, Sutcu Imam University, 46100 Kahramanmaras (Turkey); Yildirim, Ozlem [Chemistry Department, Arts and Sciences Faculty, Cukurova University, 01330 Balcali, Adana (Turkey)

    2011-02-15

    This study aimed to identify degradation intermediates and to investigate the stoichiometry of decolorization and degradation, decolorization kinetics, and removal of antibacterial activity of malachite green (MG) using ozonization processes. The decolorization of MG was optimal at an acidic pH value of 3 based on molecular ozone attack on MG molecules. The stoichiometric ratio of decolorization between ozone and MG was calculated to be 7.0 with a regression coefficient of 0.995, whereas the ratio for degradation was calculated as 13.1 with a regression coefficient of 0.998. With MG concentrations in the range of 0.30-1.82 mM, the concentration of decolorized MG increased with higher initial concentrations of MG, whereas the ozonolytic decolorization rates of MG, decreased with increasing initial concentration. The pseudo-first-order degradation rate constants (k') decreased with the initial concentration and ranged from 0.769 to 0.223 min{sup -1}. Twelve different intermediates were produced during the ozonation of MG with ozonation times between 5 min and 30 min and were identified by GC-MS. Although 86% of MG in the reaction mixture was removed by ozonation after 10 min, the decrease of antibacterial activity was very low (10%) for Bacillus subtilis and Staphylococcus epidermidis because the degradation intermediates, phenol and benzoic acid, also have antibacterial activity. The antibacterial activity of both MG and its intermediates were removed successfully with ozonation times above 26 min.

  19. Decolorization of malachite green, decolorization kinetics and stoichiometry of ozone-malachite green and removal of antibacterial activity with ozonation processes

    International Nuclear Information System (INIS)

    Kusvuran, Erdal; Gulnaz, Osman; Samil, Ali; Yildirim, Ozlem

    2011-01-01

    This study aimed to identify degradation intermediates and to investigate the stoichiometry of decolorization and degradation, decolorization kinetics, and removal of antibacterial activity of malachite green (MG) using ozonization processes. The decolorization of MG was optimal at an acidic pH value of 3 based on molecular ozone attack on MG molecules. The stoichiometric ratio of decolorization between ozone and MG was calculated to be 7.0 with a regression coefficient of 0.995, whereas the ratio for degradation was calculated as 13.1 with a regression coefficient of 0.998. With MG concentrations in the range of 0.30-1.82 mM, the concentration of decolorized MG increased with higher initial concentrations of MG, whereas the ozonolytic decolorization rates of MG, decreased with increasing initial concentration. The pseudo-first-order degradation rate constants (k') decreased with the initial concentration and ranged from 0.769 to 0.223 min -1 . Twelve different intermediates were produced during the ozonation of MG with ozonation times between 5 min and 30 min and were identified by GC-MS. Although 86% of MG in the reaction mixture was removed by ozonation after 10 min, the decrease of antibacterial activity was very low (10%) for Bacillus subtilis and Staphylococcus epidermidis because the degradation intermediates, phenol and benzoic acid, also have antibacterial activity. The antibacterial activity of both MG and its intermediates were removed successfully with ozonation times above 26 min.

  20. Two-Step Production of Phenylpyruvic Acid from L-Phenylalanine by Growing and Resting Cells of Engineered Escherichia coli: Process Optimization and Kinetics Modeling

    Science.gov (United States)

    Hou, Ying; Hossain, Gazi Sakir; Li, Jianghua; Shin, Hyun-dong; Liu, Long; Du, Guocheng; Chen, Jian

    2016-01-01

    Phenylpyruvic acid (PPA) is widely used in the pharmaceutical, food, and chemical industries. Here, a two-step bioconversion process, involving growing and resting cells, was established to produce PPA from l-phenylalanine using the engineered Escherichia coli constructed previously. First, the biotransformation conditions for growing cells were optimized (l-phenylalanine concentration 20.0 g·L−1, temperature 35°C) and a two-stage temperature control strategy (keep 20°C for 12 h and increase the temperature to 35°C until the end of biotransformation) was performed. The biotransformation conditions for resting cells were then optimized in 3-L bioreactor and the optimized conditions were as follows: agitation speed 500 rpm, aeration rate 1.5 vvm, and l-phenylalanine concentration 30 g·L−1. The total maximal production (mass conversion rate) reached 29.8 ± 2.1 g·L−1 (99.3%) and 75.1 ± 2.5 g·L−1 (93.9%) in the flask and 3-L bioreactor, respectively. Finally, a kinetic model was established, and it was revealed that the substrate and product inhibition were the main limiting factors for resting cell biotransformation. PMID:27851793

  1. Hydroxylamine derivative in Purex process. Part 8. The kinetics and mechanism of the redox reaction of N-methylhydroxylamine and vanadium(V)

    International Nuclear Information System (INIS)

    Anyun Zhang; Shaanxi Normal Univ., Xi'an; Kai Li; Jingxin Hu

    2004-01-01

    The kinetic properties of the oxidation-reduction reaction between N-methylhydroxylamine (NMHAN) and vanadium(V) in nitric acid medium has been studied by spectrophotometry at 23.1 deg C. The rate equation of the redox reaction was determined as -d[V(V)]/dt = k[V(V)] [NMHAN] by investigating the influence of concentration of NMHAN, acidity, ionic strength and the ratio of initial concentration of V(V) to NMHAN on the reaction. The rate constant of the reaction k = 0.818 ± 0.051 (mol/l) -1 x s -1 at the ionic strength of 1.00 mol/l. The activation energy of the redox reaction was calculated to be 39.6 kJ/mol. A possibly radical mechanism of the redox reaction between NMHAN and V(V) has been suggested on the basis of electron spin resonance (ESR) spectra of nitroxyl radical, i.e., CH 3 NHO. It is helpful to understand and make the redox mechanism of NMHAN and Np(VI) clear in the reprocessing process of nuclear spent fuel. (author)

  2. Crystallization kinetics and growth mechanism of 8 mol% yttria-stabilized zirconia (8YSZ) nano-powders prepared by a sol-gel process

    Energy Technology Data Exchange (ETDEWEB)

    Kuo, C.-W. [Department of Resources Engineering, National Cheng Kung University, 1 Ta-Hsueh Road, Tainan 70101, Taiwan (China); Lee, Y.-H. [Department of Materials Science and Engineering, National Cheng Kung University, 1 Ta-Hsueh Road, Tainan 70101, Taiwan (China); Hung, I-M. [Department of Chemical Engineering and Materials Science, Yuan Ze University, 135 Far-East Road, Chung-Li, Taoyuan, Taiwan (China); Wang, M.-C. [Faculty of Fragrance and Cosmetics, Kaohsiung Medical University, 100 Shi-Chuan 1st Road, Kaohsiung 807, Taiwan (China); Wen, S.-B. [Department of Resources Engineering, National Cheng Kung University, 1 Ta-Hsueh Road, Tainan 70101, Taiwan (China); Fung, K.-Z. [Department of Materials Science and Engineering, National Cheng Kung University, 1 Ta-Hsueh Road, Tainan 70101, Taiwan (China); Shih, C.-J. [Faculty of Fragrance and Cosmetics, Kaohsiung Medical University, 100 Shi-Chuan 1st Road, Kaohsiung 807, Taiwan (China)], E-mail: cjshih@kmu.edu.tw

    2008-04-03

    Eight mol% yttria-stabilized zirconia (8YSZ) gel powders were synthesized at 348 K for 2 h using ZrOCl{sub 2}.8H{sub 2}O and Y(NO{sub 3}){sub 3}.6H{sub 2}O as starting materials in an ethanol-water solution by a sol-gel process. The crystallization kinetics and growth mechanism of the 8YSZ gel powders have been investigated using differential thermal analysis (DTA), X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and selected area electron diffraction (SAED). The XRD results and SAED pattern show that the 8YSZ gel powders calcined at 773 K for 2 h is a cubic ZrO{sub 2}. The activation energy for the crystallization of the cubic ZrO{sub 2} formation in the 8YSZ gel powders is determined as 231.76 kJ/mol by a non-isothermal DTA method. Both growth morphology parameter (n) and crystallization mechanism index (m) are close to 3.0, indicating that the bulk nucleation is dominant in the cubic ZrO{sub 2} formation. The TEM examination shows that the cubic ZrO{sub 2} has a spherical-like morphology with a size ranging from 10 to 20 nm.

  3. Crystallization kinetics and growth mechanism of 8 mol% yttria-stabilized zirconia (8YSZ) nano-powders prepared by a sol-gel process

    International Nuclear Information System (INIS)

    Kuo, C.-W.; Lee, Y.-H.; Hung, I-M.; Wang, M.-C.; Wen, S.-B.; Fung, K.-Z.; Shih, C.-J.

    2008-01-01

    Eight mol% yttria-stabilized zirconia (8YSZ) gel powders were synthesized at 348 K for 2 h using ZrOCl 2 .8H 2 O and Y(NO 3 ) 3 .6H 2 O as starting materials in an ethanol-water solution by a sol-gel process. The crystallization kinetics and growth mechanism of the 8YSZ gel powders have been investigated using differential thermal analysis (DTA), X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and selected area electron diffraction (SAED). The XRD results and SAED pattern show that the 8YSZ gel powders calcined at 773 K for 2 h is a cubic ZrO 2 . The activation energy for the crystallization of the cubic ZrO 2 formation in the 8YSZ gel powders is determined as 231.76 kJ/mol by a non-isothermal DTA method. Both growth morphology parameter (n) and crystallization mechanism index (m) are close to 3.0, indicating that the bulk nucleation is dominant in the cubic ZrO 2 formation. The TEM examination shows that the cubic ZrO 2 has a spherical-like morphology with a size ranging from 10 to 20 nm

  4. Sorption of water alkalinity and hardness from high-strength wastewater on bifunctional activated carbon: process optimization, kinetics and equilibrium studies.

    Science.gov (United States)

    Amosa, Mutiu K

    2016-08-01

    Sorption optimization and mechanism of hardness and alkalinity on bifunctional empty fruit bunch-based powdered activation carbon (PAC) were studied. The PAC possessed both high surface area and ion-exchange properties, and it was utilized in the treatment of biotreated palm oil mill effluent. Batch adsorption experiments designed with Design Expert(®) were conducted in correlating the singular and interactive effects of the three adsorption parameters: PAC dosage, agitation speed and contact time. The sorption trends of the two contaminants were sequentially assessed through a full factorial design with three factor interaction models and a central composite design with polynomial models of quadratic order. Analysis of variance revealed the significant factors on each design response with very high R(2) values indicating good agreement between model and experimental values. The optimum operating conditions of the two contaminants differed due to their different regions of operating interests, thus necessitating the utility of desirability factor to get consolidated optimum operation conditions. The equilibrium data for alkalinity and hardness sorption were better represented by the Langmuir isotherm, while the pseudo-second-order kinetic model described the adsorption rates and behavior better. It was concluded that chemisorption contributed majorly to the adsorption process.

  5. Oxidative desulfurization: kinetic modelling.

    Science.gov (United States)

    Dhir, S; Uppaluri, R; Purkait, M K

    2009-01-30

    Increasing environmental legislations coupled with enhanced production of petroleum products demand, the deployment of novel technologies to remove organic sulfur efficiently. This work represents the kinetic modeling of ODS using H(2)O(2) over tungsten-containing layered double hydroxide (LDH) using the experimental data provided by Hulea et al. [V. Hulea, A.L. Maciuca, F. Fajula, E. Dumitriu, Catalytic oxidation of thiophenes and thioethers with hydrogen peroxide in the presence of W-containing layered double hydroxides, Appl. Catal. A: Gen. 313 (2) (2006) 200-207]. The kinetic modeling approach in this work initially targets the scope of the generation of a superstructure of micro-kinetic reaction schemes and models assuming Langmuir-Hinshelwood (LH) and Eley-Rideal (ER) mechanisms. Subsequently, the screening and selection of above models is initially based on profile-based elimination of incompetent schemes followed by non-linear regression search performed using the Levenberg-Marquardt algorithm (LMA) for the chosen models. The above analysis inferred that Eley-Rideal mechanism describes the kinetic behavior of ODS process using tungsten-containing LDH, with adsorption of reactant and intermediate product only taking place on the catalyst surface. Finally, an economic index is presented that scopes the economic aspects of the novel catalytic technology with the parameters obtained during regression analysis to conclude that the cost factor for the catalyst is 0.0062-0.04759 US $ per barrel.

  6. Oxidative desulfurization: Kinetic modelling

    International Nuclear Information System (INIS)

    Dhir, S.; Uppaluri, R.; Purkait, M.K.

    2009-01-01

    Increasing environmental legislations coupled with enhanced production of petroleum products demand, the deployment of novel technologies to remove organic sulfur efficiently. This work represents the kinetic modeling of ODS using H 2 O 2 over tungsten-containing layered double hydroxide (LDH) using the experimental data provided by Hulea et al. [V. Hulea, A.L. Maciuca, F. Fajula, E. Dumitriu, Catalytic oxidation of thiophenes and thioethers with hydrogen peroxide in the presence of W-containing layered double hydroxides, Appl. Catal. A: Gen. 313 (2) (2006) 200-207]. The kinetic modeling approach in this work initially targets the scope of the generation of a superstructure of micro-kinetic reaction schemes and models assuming Langmuir-Hinshelwood (LH) and Eley-Rideal (ER) mechanisms. Subsequently, the screening and selection of above models is initially based on profile-based elimination of incompetent schemes followed by non-linear regression search performed using the Levenberg-Marquardt algorithm (LMA) for the chosen models. The above analysis inferred that Eley-Rideal mechanism describes the kinetic behavior of ODS process using tungsten-containing LDH, with adsorption of reactant and intermediate product only taking place on the catalyst surface. Finally, an economic index is presented that scopes the economic aspects of the novel catalytic technology with the parameters obtained during regression analysis to conclude that the cost factor for the catalyst is 0.0062-0.04759 US $ per barrel

  7. Crystallite growth kinetics of TiO{sub 2} surface modification with 9 mol% ZnO prepared by a coprecipitation process

    Energy Technology Data Exchange (ETDEWEB)

    Ko, Horng-Huey [Department of Fragrance and Cosmetic Science, Kaohsiung Medical University, 100 Shih-Chuan 1st Road, Kaohsiung 80708, Taiwan (China); Hsi, Chi-Shiung [Department of Materials Science and Engineering, National United University, 1 Lein-Da, Kung-Ching Li, Miao-Li 36003, Taiwan (China); Wang, Moo-Chin, E-mail: mcwang@kmu.edu.tw [Department of Fragrance and Cosmetic Science, Kaohsiung Medical University, 100 Shih-Chuan 1st Road, Kaohsiung 80708, Taiwan (China); Zhao, Xiujian, E-mail: opluse@whut.edu.cn [State Key Laboratory of Silicate Materials for Architectures, Wuhan University of Technology, Wuhan 430070 (China)

    2014-03-05

    Highlights: • TiO{sub 2} powder surface modification with 9 mol% ZnO was obtained. • Phase transformation from anatase to rutile was hindered by ZnO added. • Growth kinetic of anatase TiO{sub 2} nanocrystallites in T-9Z powders was described as: D{sub A,9}{sup 2}=2.42×10{sup 5}×exp(-39.9×10{sup 3}/RT). • Growth kinetic of rutile TiO{sub 2} nanocrystallites in T-9Z powders was described as: D{sub R,9}{sup 2}=8.49×10{sup 5}×exp(-47.6×10{sup 3}/RT) rutile TiO{sub 2}. -- Abstract: The nanocrystallite growth of TiO{sub 2} surface modification with 9 mol% ZnO prepared by a coprecipitation process has been studied. Thermogravimetric and differential thermal analysis (TG/DTA), X-ray diffraction (XRD), transmission electron microscopy (TEM), selected area electron diffraction (SAED) and UV–VIS–NIR spectrophotometry have been utilized to characterize the TiO{sub 2} nanocrystallites surface modification with 9 mol% ZnO (denoted by T-9Z). The DTA result shows that the anatase TiO{sub 2} first formed at 533 K and the completion of anatase TiO{sub 2} crystallization occurred at 745 K for the T-9Z freeze-dried precursor powders. XRD results reveal that the anatase and rutile TiO{sub 2} coexist when the T-9Z freeze-dried precursor powders were calcined at 523–973 K for 2 h. When the T-9Z freeze-dried precursor powders were calcined at 973 K for 2 h, rutile TiO{sub 2} was the major phase, and the minor phases were anatase TiO{sub 2} and Zn{sub 2}Ti{sub 3}O{sub 8}. The phase was composed of the rutile TiO{sub 2} and Zn{sub 2}TiO{sub 4} for the T-9Z freeze-dried precursor powders after calcination at 1273 K for 2 h. The growth kinetics of TiO{sub 2} nanocrystallites in T-9Z powders were described as: D{sub A,9}{sup 2}=2.42×10{sup 5}×exp(-39.9×10{sup 3}/RT)and D{sub R,9}{sup 2}=8.49×10{sup 5}×exp(-47.6×10{sup 3}/RT) for anatase and rutile TiO{sub 2} nanocrystallites respectively. The analysis results of UV/VIS/NIR spectra reveal that the T-9Z freeze

  8. Kinetic energy absorbing pad

    International Nuclear Information System (INIS)

    Bricmont, R.J.; Hamilton, P.A.; Ming Long Ting, R.

    1981-01-01

    Reactors, fuel processing plants etc incorporate pipes and conduits for fluids under high pressure. Fractures, particularly adjacent to conduit elbows, produce a jet of liquid which whips the broken conduit at an extremely high velocity. An enormous impact load would be applied to any stationary object in the conduit's path. The design of cellular, corrugated metal impact pads to absorb the kinetic energy of the high velocity conduits is given. (U.K.)

  9. Report - Production of Gasoline and Diesel from Biomass via Fast Pyrolysis, Hydrotreating and Hydrocracking: A Design Case

    Energy Technology Data Exchange (ETDEWEB)

    Jones, S. B. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Valkenburg, C. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Walton, C. W. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Elliott, D. C. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Holladay, J. E. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Stevens, D. J. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Kinchin, C. [National Renewable Energy Lab. (NREL), Golden, CO (United States); Czernik, S. [National Renewable Energy Lab. (NREL), Golden, CO (United States)

    2009-02-01

    The purpose of this design case study is to evaluate a processing pathway for converting biomass into infrastructure-compatible hydrocarbon biofuels. This design case investigates production of fast pyrolysis oil from biomass and the upgrading of that bio-oil as a means for generating infrastructure-ready renewable gasoline and diesel fuels.

  10. Thermodynamics and Kinetics of Sulfide Oxidation by Oxygen: A Look at Inorganically Controlled Reactions and Biologically Mediated Processes in the Environment

    Science.gov (United States)

    Luther, George W.; Findlay, Alyssa J.; MacDonald, Daniel J.; Owings, Shannon M.; Hanson, Thomas E.; Beinart, Roxanne A.; Girguis, Peter R.

    2011-01-01

    The thermodynamics for the first electron transfer step for sulfide and oxygen indicates that the reaction is unfavorable as unstable superoxide and bisulfide radical ions would need to be produced. However, a two-electron transfer is favorable as stable S(0) and peroxide would be formed, but the partially filled orbitals in oxygen that accept electrons prevent rapid kinetics. Abiotic sulfide oxidation kinetics improve when reduced iron and/or manganese are oxidized by oxygen to form oxidized metals which in turn oxidize sulfide. Biological sulfur oxidation relies on enzymes that have evolved to overcome these kinetic constraints to affect rapid sulfide oxidation. Here we review the available thermodynamic and kinetic data for H2S and HS• as well as O2, reactive oxygen species, nitrate, nitrite, and NOx species. We also present new kinetic data for abiotic sulfide oxidation with oxygen in trace metal clean solutions that constrain abiotic rates of sulfide oxidation in metal free solution and agree with the kinetic and thermodynamic calculations. Moreover, we present experimental data that give insight on rates of chemolithotrophic and photolithotrophic sulfide oxidation in the environment. We demonstrate that both anaerobic photolithotrophic and aerobic chemolithotrophic sulfide oxidation rates are three or more orders of magnitude higher than abiotic rates suggesting that in most environments biotic sulfide oxidation rates will far exceed abiotic rates due to the thermodynamic and kinetic constraints discussed in the first section of the paper. Such data reshape our thinking about the biotic and abiotic contributions to sulfide oxidation in the environment. PMID:21833317

  11. Simultaneous application of microwave energy and hot air to whole drying process of apple slices: drying kinetics, modeling, temperature profile and energy aspect

    Science.gov (United States)

    Horuz, Erhan; Bozkurt, Hüseyin; Karataş, Haluk; Maskan, Medeni

    2018-02-01

    Drying kinetics, modeling, temperature profile and energy indices were investigated in apple slices during drying by a specially designed microwave-hot air domestic hybrid oven at the following conditions: 120, 150 and 180 W microwave powers coupled with 50, 60 and 70 °C air temperatures. Both sources of energy were applied simultaneously during the whole drying processes. The drying process continued until the moisture content of apple slices reached to 20% from 86.3% (wet basis, w.b). Drying times ranged from 330 to 800 min and decreased with increasing microwave power and air temperatures. The constant rate period was only observed at low microwave powers and air temperatures. Two falling rate periods were observed. Temperature of apple slices sharply increased within the first 60 min, then reached equilibrium with drying medium and finally increased at the end of the drying process. In order to describe drying behavior of apple slices nine empirical models were applied. The Modified Logistic Model fitted the best our experimental data ( R 2 = 0.9955-0.9998; χ 2 = 3.46 × 10-5-7.85 × 10-4 and RMSE = 0.0052-0.0221). The effective moisture and thermal diffusivities were calculated by Fick's second law and ranged from 1.42 × 10-9 to 3.31 × 10-9 m2/s and 7.70 × 10-9 to 12.54 × 10-9 m2/s, respectively. The activation energy ( Ea) values were calculated from effective moisture diffusivity ( Deff), thermal diffusivity ( α) and the rate constant of the best model ( k). The Ea values found from these three terms were similar and varied from 13.04 to 33.52 kJ/mol. Energy consumption and specific energy requirement of the hybrid drying of apple slices decreased and energy efficiency of the drying system increased with increasing microwave power and air temperature. Apples can be dried rapidly and effectively by use of the hybrid technique.

  12. Characterization of catalysts by Moessbauer spectroscopy: An application to the study of Fischer-Tropsch, hydrotreating and super Claus catalysts

    International Nuclear Information System (INIS)

    Kraan, A.M. van der; Boellaard, E.; Craje, M.W.J.

    1993-01-01

    Moessbauer spectroscopy is an excellent in-situ technique for the identification of phases present in catalysts. Applied to metallic iron catalysts used in the Fischer-Tropsch reaction it reveals a detailed picture of the carburization process and provides insight into the relation between the properties of the catalytic material and its activity. The influence of a support and the effect of alloying iron with an (in)active metal on the catalytic performance is discussed for Fe, Cu-Fe and Ni-Fe systems. In addition, Moessbauer spectroscopy is used for the identification of 'Co-sulfide' species present in sulfided Co and CoMo catalysts applied in one of the largest chemical processes in the world, the hydrotreatment of crude oil. A structural model is proposed. Finally, the contribution of Moessbauer spectroscopic studies to the development of a new catalyst for cleaning of Claus tail gas via selective oxidation of hydrogen sulfide to elemental sulfur is discussed. (orig.)

  13. Transformation kinetics for nucleus clusters

    International Nuclear Information System (INIS)

    Villa, Elena; Rios, Paulo R.

    2009-01-01

    A rigorous mathematical approach based on stochastic geometry concepts is presented to extend previous Johnson-Mehl, Avrami, Kolmogorov treatment of transformation kinetics to situations in which nuclei are not homogeneously located in space but are located in clusters. An exact analytical solution is presented here for the first time assuming that nucleation sites follow a Matern cluster process. The influence of Matern cluster process parameters on subsequent growth kinetics and the microstructural path are illustrated by means of numerical examples. Moreover, using the superposition principle, exact analytical solutions are also obtained when nucleation takes place by a combination of a Matern cluster process and an inhomogeneous Poisson point process. The new solutions presented here significantly increase the number of exactly solvable cases available to formal kinetics.

  14. Kinetics and mechanism of elementary chemical processes of importance in combustion. Periodic report 2 for the period October 1986 - April 1987

    International Nuclear Information System (INIS)

    Munk, J.; Pagsberg, P.; Ratajczak, E.; Sillesen, A.

    1987-04-01

    UV-spectra of vinyl and propargyl radicals have been recorded employing the technique of pulse radiolysis combined with time resolved UV-absorption spectroscoppy. The kinetics of vinyl radiocals was studied by monitoring the transient absorption signals in the range of 215-230 nm. In the presence of oxygen we observed the build-up of strong transient absorption signals at 230nm. Based on analysis of the spectral and kinetic features we have tentatively assigned the new absorption band to the vinyl peroxy radical. Propargyl radicals were produced by the argon sensitized radiolysis of propargyl bromide. In addition to the well-known absorption band at 332 nm we have observed a much stronger band with a maximum at 250 nm. The observed second order decay kinetics is accounted for by the combination reactions 2 C x H x -> products and C 3 H 3 + Br -> C 3 H 3 Br. (EG)

  15. Process Design and Economics for the Conversion of Lignocellulosic Biomass to Hydrocarbons: Dilute-Acid and Enzymatic Deconstruction of Biomass to Sugars and Biological Conversion of Sugars to Hydrocarbons

    Energy Technology Data Exchange (ETDEWEB)

    Davis, R.; Tao, L.; Tan, E. C. D.; Biddy, M. J.; Beckham, G. T.; Scarlata, C.; Jacobson, J.; Cafferty, K.; Ross, J.; Lukas, J.; Knorr, D.; Schoen, P.

    2013-10-01

    This report describes one potential conversion process to hydrocarbon products by way of biological conversion of lingnocellulosic-dervied sugars. The process design converts biomass to a hydrocarbon intermediate, a free fatty acid, using dilute-acid pretreatement, enzymatic saccharification, and bioconversion. Ancillary areas--feed handling, hydrolysate conditioning, product recovery and upgrading (hydrotreating) to a final blendstock material, wastewater treatment, lignin combusion, and utilities--are also included in the design.

  16. Kinetic parameters from thermogravimetric analysis

    Science.gov (United States)

    Kiefer, Richard L.

    1993-01-01

    High performance polymeric materials are finding increased use in aerospace applications. Proposed high speed aircraft will require materials to withstand high temperatures in an oxidative atmosphere for long periods of time. It is essential that accurate estimates be made of the performance of these materials at the given conditions of temperature and time. Temperatures of 350 F (177 C) and times of 60,000 to 100,000 hours are anticipated. In order to survey a large number of high performance polymeric materials on a reasonable time scale, some form of accelerated testing must be performed. A knowledge of the rate of a process can be used to predict the lifetime of that process. Thermogravimetric analysis (TGA) has frequently been used to determine kinetic information for degradation reactions in polymeric materials. Flynn and Wall studied a number of methods for using TGA experiments to determine kinetic information in polymer reactions. Kinetic parameters, such as the apparent activation energy and the frequency factor, can be determined in such experiments. Recently, researchers at the McDonnell Douglas Research Laboratory suggested that a graph of the logarithm of the frequency factor against the apparent activation energy can be used to predict long-term thermo-oxidative stability for polymeric materials. Such a graph has been called a kinetic map. In this study, thermogravimetric analyses were performed in air to study the thermo-oxidative degradation of several high performance polymers and to plot their kinetic parameters on a kinetic map.

  17. Characterization of upgraded fast pyrolysis oak oil distillate fractions from sulfided and non-sulfided catalytic hydrotreating

    Energy Technology Data Exchange (ETDEWEB)

    Olarte, Mariefel V.; Padmaperuma, Asanga B.; Ferrell, Jack R.; Christensen, Earl D.; Hallen, Richard T.; Lucke, Richard B.; Burton, Sarah D.; Lemmon, Teresa L.; Swita, Marie S.; Fioroni, Gina; Elliott, Douglas C.; Drennan, Corinne

    2017-08-01

    Catalytic hydroprocessing of pyrolysis oils from biomass produces hydrocarbons that can be considered for liquid fuel production. This process requires removal of oxygen and cracking of the heavier molecular weight bio-oil constituents into smaller fragments at high temperatures and pressures under hydrogen. A comprehensive understanding of product oils is useful to optimize cost versus degree of deoxygenation. Additionally, a better understanding of the chemical composition of the distillate fractions can open up other uses of upgraded oils for potentially higher-value chemical streams. We present in this paper the characterization data for five well-defined distillate fractions of two hydroprocessed oils with different oxygen levels: a low oxygen content (LOC, 1.8% O, wet basis) oil and a medium oxygen content (MOC, 6.4% O, wet basis) oil. Elemental analysis and 13C NMR results suggest that the distillate fractions become more aromatic/unsaturated as they become heavier. Our results also show that the use of sulfided catalysts directly affects the S content of the lightest distillate fraction. Carbonyl and carboxylic groups were found in the MOC light fractions, while phenols were present in the heavier fractions for both MOC and LOC. PIONA analysis of the light LOC fraction shows a predominance of paraffins with a minor amount of olefins. These results can be used to direct future research on refinery integration and production of value-added product from specific upgraded oil streams.

  18. Sensitivity of Technical Choices on the GHG Emissions and Expended Energy of Hydrotreated Renewable Jet Fuel from Microalgae

    Directory of Open Access Journals (Sweden)

    Patouillard Laure

    2016-01-01

    Full Text Available Taking into account the environmental impacts of biofuel production is essential to develop new and innovative low-emission processes. The assessment of life cycle GreenHouse Gas (GHG emissions of biofuel is mandatory for the countries of the European Union. New biomass resources that hardly compete with food crops are been developed increasingly. Microalgae are an interesting alternative to terrestrial biomass thanks to their high photosynthetic efficiency and their ability to accumulate lipids. This article provides an analysis of potential environmental impacts of the production of algal biofuel for aviation using the Life Cycle Assessment (LCA. Evaluated impacts are GHG emissions and the primary energy consumption, from extraction of raw materials to final waste treatment. This study compared two management choices for oilcakes generated after oil extraction from microalgae. In the first system, these cakes are treated by energetic allocation and in the second by anaerobic digestion. In both cases, the steps of cultivation and harvesting have the highest impact on the results. Sensitivity analyzes are performed on technical choices of operating systems (choice of the type of nutrients, mode of harvesting, drying and oil extraction as well as a Monte-Carlo analysis on key parameter values for GHG emissions (concentration of microalgae in ponds, productivity and oil content. The results highlight the impact of the use of chemical fertilizers and the importance of the concentration of algae on GHG emissions and energy consumption.

  19. Tantalum high-temperature oxidation kinetics

    International Nuclear Information System (INIS)

    Grigor'ev, Yu.M.; Sarkisyan, A.A.; Merzhanov, A.G.

    1981-01-01

    Kinetics of heat release and scale growth during tantalum oxidation within 650-1300 deg C temperature range in oxygen-containing media is investigated. Kinetic equations and temperature and pressure dependences of constants are ound Applicability of the kinetic Lorie mechanism for the description of the tantalum oxidation kinetics applicably to rapid-passing processes is shown. It is stated that the process rate (reaction ability) is determined by adsorption desorption factors on the external surface of the ''protective'' oxide for the ''linear'' oxidation stage [ru

  20. Kinetics of nickel bioaccumulation and its relevance to selected cellular processes in leaves of Elodea canadensis during short-term exposure.

    Science.gov (United States)

    Maleva, Maria G; Malec, Przemysław; Prasad, Majeti Narasimha Vara; Strzałka, Kazimierz

    2016-03-01

    Elodea canadensis is an aquatic macrophyte used widely as a bioindicator for the monitoring of water quality and in the phytoremediation of metal-contaminated waters. This study considers the kinetics of nickel bioaccumulation and changes in accompanying metabolic and stress-related physiological parameters. These include photosynthetic activity, pigment content, the accumulation of thiol-containing compounds, thiobarbituric acid-reactive substance (TBARS) products, and the activity of selected antioxidant enzymes (catalase, glutathione reductase, superoxide dismutase). Elodea leaves accumulated nickel according to pseudo-second-order kinetics, and the protective responses followed a time sequence which was related to the apparent rates of nickel accumulation. The applicability of second-order kinetics to the Ni uptake by Elodea leaves during the first 8 h of exposure to the metal suggested that the passive binding of metal ions (chemisorption) was a rate-limiting step at the initial phase of Ni accumulation. This phase was accompanied by an increase in photosynthetic activity together with elevated photosynthetic pigments and protein synthesis, the enhanced activity of antioxidant enzymes, and increased thiol concentration. In contrast, there was a decrease in metabolic activity upon the accumulation of TBARS, and the decline in enzyme activity was observed in the saturation phase of Ni accumulation (8-24 h). These results show that a correlation exists between the protective response and the apparent kinetic rate of Ni uptake. Thus, the time of exposure to the toxicant is a crucial factor in the activation of specific mechanisms of Ni detoxification and stress alleviation.

  1. Kinetic removal of haloacetonitrile precursors by photo-based advanced oxidation processes (UV/H2O2, UV/O3, and UV/H2O2/O3).

    Science.gov (United States)

    Srithep, Sirinthip; Phattarapattamawong, Songkeart

    2017-06-01

    The objective of the study is to evaluate the performance of conventional treatment process (i.e., coagulation, flocculation, sedimentation and sand filtration) on the removals of haloacetonitrile (HAN) precursors. In addition, the removals of HAN precursors by photo-based advanced oxidation processes (Photo-AOPs) (i.e., UV/H 2 O 2 , UV/O 3 , and UV/H 2 O 2 /O 3 ) are investigated. The conventional treatment process was ineffective to remove HAN precursors. Among Photo-AOPs, the UV/H 2 O 2 /O 3 was the most effective process for removing HAN precursors, followed by UV/H 2 O 2 , and UV/O 3 , respectively. For 20min contact time, the UV/H 2 O 2 /O 3 , UV/H 2 O 2 , and UV/O 3 suppressed the HAN formations by 54, 42, and 27% reduction. Increasing ozone doses from 1 to 5 mgL -1 in UV/O 3 systems slightly improved the removals of HAN precursors. Changes in pH (6-8) were unaffected most of processes (i.e., UV, UV/H 2 O 2 , and UV/H 2 O 2 /O 3 ), except for the UV/O 3 system that its efficiency was low in the weak acid condition. The pseudo first-order kinetic constant for removals of dichloroacetonitrile precursors (k' DCANFP ) by the UV/H 2 O 2 /O 3 , UV/H 2 O 2 and standalone UV systems were 1.4-2.8 orders magnitude higher than the UV/O 3 process. The kinetic degradation of dissolved organic nitrogen (DON) tended to be higher than the k' DCANFP value. This study firstly differentiates the kinetic degradation between DON and HAN precursors. Copyright © 2017 Elsevier Ltd. All rights reserved.

  2. The role of antiphase boundaries in the kinetic process of the L12→ D022 structural change of an Ni3Al0.45V0.50 alloy

    International Nuclear Information System (INIS)

    Tanimura, Makoto; Koyama, Yasumasa

    2006-01-01

    The influence of antiphase boundaries (APBs) on the kinetic process of the L1 2 → D0 22 structural change in an Ni 3 Al 0.45 V 0.50 alloy has been investigated by transmission electron microscopy. The structural change includes two kinetic factors, i.e., the periodic introduction of antiphase-shifted planes (APSPs) in the L1 2 structure and V diffusion in the L1 2 matrix. Our results revealed that APB migration was accompanied by V diffusion as if to sweep the V atoms out of the antiphase domains (APDs). It was also found that the APBs served as the nucleation sites of the D0 22 regions, because the combination of the migrated APBs produced the APSPs in the L1 2 structure. On this basis, it is proposed that the APBs bring together the two kinetic factors in the process of the L1 2 → D0 22 structural change, the physical origin of which is the variation in the charge density distribution of the APDs due to APB migration

  3. Biodiesel via hydrotreating of fat

    DEFF Research Database (Denmark)

    Madsen, Anders Theilgaard; Ahmed, El Hadi; Christensen, Claus Hviid

    Biodiesel production via transesterification to fatty acid alkyl esters is rising rapidly worldwide due to the limited availability of fossil resources and the problems of global warming. Often, however, the use of 2nd-generation feedstock like animal waste fat and trap greases etc. is made...

  4. Process optimization and leaching kinetics of zinc and manganese metals from zinc-carbon and alkaline spent batteries using citric acid reagent

    Science.gov (United States)

    Yuliusman; Amiliana, R. A.; Wulandari, P. T.; Huda, M.; Kusumadewi, F. A.

    2018-03-01

    Zn-Carbon and Alkaline spent batteries contains heavy metals, such as zinc and manganese, which can causes environmental problem if not handled properly. Usually the recovery of these metals were done by leaching method using strong acid, but the use of strong acids as leaching reagents can be harmful to the environment. This paper concerns the recovery of Zn and Mn metals from Zn-C and alkaline spent batteries with leaching method using citric acid as the environmental friendly leaching reagent. The leaching conditions using citric acid were optimized and the leaching kinetics of Zn and Mn in citric acid solution was investigated. The leaching of 89.62% Zn and 63.26% Mn was achieved with 1.5 M citric acid, 90°C temperature, and 90 minutes stirring time. Kinetics data for the dissolution of Zn showed the best fit to chemical control shrinking core model, while the diffusion controlled model was suitable for the dissolution of Mn kinetics data. The activation energy of 6.12 and 1.73 kcal/mol was acquired for the leaching of Zn and Mn in the temperature range 60°C-90°C.

  5. A Kinetic Model for β-Amyloid Adsorption at the Air/Solution Interface and Its Implication to the β-Amyloid Aggregation Process

    Science.gov (United States)

    Jiang, Dianlu; Dinh, Kim Lien; Ruthenburg, Travis; Zhang, Yi; Su, Lei; Land, Donald; Zhou, Feimeng

    2011-01-01

    The kinetics of adsorption at the air/buffer solution interface of amyloid beta peptide, Aβ(1–42), whose bulk concentration (submicromolar) is more than two orders of magnitude lower than that typically used in other in vitro aggregation studies, has been studied using a Langmuir-Blodgett trough. The pressure–time curves exhibit a lag phase, wherein the surface pressure essentially remains at zero, and a rising phase, corresponding to the Aβ adsorption at the interface. The duration of the lag phase was found to be highly dependent on both the Aβ bulk concentration and the solution temperature. A large activation energy (62.2 ± 4.1 KJ/mol) was determined and the apparent adsorption rate constant was found to be linearly dependent on the Aβ bulk concentration. Attenuated total reflection-IR spectra of the adsorbed Aβ transferred to a solid substrate and circular dichroism measurements of Aβ in the solution layer near the interface reveal that the natively unstructured Aβ in the bulk undergo a conformation change (folding) to mainly the α-helical structure. The results suggest that, prior to the adsorption step, an equilibrium between Aβ conformations is established within the subsurface. The kinetic equation derived from this model confirms that the overall Aβ adsorption is kinetically controlled and the apparent rate constant is proportional to the Aβ bulk concentration. This model also indicates that interfaces such as cell membranes and lipid bilayers may facilitate Aβ aggregation/fibrillation by providing a thin hydrophobic layer adjacent to the interface for the initial Aβ conformation change (misfolding) and accumulation. Such a preconcentration effect offers a plausible explanation of the fact that Aβ fibrillation occurs in vivo at nanomolar concentrations. Another important biological implication from our work is that Aβ misfolding may occur before its adsorption onto a cell membrane. This general kinetic model should also find

  6. A kinetic model for beta-amyloid adsorption at the air/solution interface and its implication to the beta-amyloid aggregation process.

    Science.gov (United States)

    Jiang, Dianlu; Dinh, Kim Lien; Ruthenburg, Travis C; Zhang, Yi; Su, Lei; Land, Donald P; Zhou, Feimeng

    2009-03-12

    At the air/buffer solution interface the kinetics of adsorption of amyloid beta peptide, Abeta(1-42), whose bulk concentration (submicromolar) is more than 2 orders of magnitude lower than that typically used in other in vitro aggregation studies, has been studied using a Langmuir-Blodgett trough. The pressure-time curves exhibit a lag phase, wherein the surface pressure essentially remains at zero, and a rising phase, corresponding to the Abeta adsorption at the interface. The duration of the lag phase was found to be highly dependent on both the Abeta bulk concentration and the solution temperature. A large activation energy (62.2 +/- 4.1 KJ/mol) was determined and the apparent adsorption rate constant was found to be linearly dependent on the Abeta bulk concentration. Attenuated total reflection-IR spectra of the adsorbed Abeta transferred to a solid substrate and circular dichroism measurements of Abeta in the solution layer near the interface reveal that the natively unstructured Abeta in the bulk undergo a conformation change (folding) to mainly the alpha-helical structure. The results suggest that, prior to the adsorption step, an equilibrium between Abeta conformations is established within the subsurface. The kinetic equation derived from this model confirms that the overall Abeta adsorption is kinetically controlled and the apparent rate constant is proportional to the Abeta bulk concentration. This model also indicates that interfaces such as cell membranes and lipid bilayers may facilitate Abeta aggregation/ fibrillation by providing a thin hydrophobic layer adjacent to the interface for the initial A/beta conformation change (misfolding) and accumulation. Such a preconcentration effect offers a plausible explanation of the fact that Abeta fibrillation occurs in vivo at nanomolar concentrations. Another important biological implication from our work is that Abeta misfolding may occur before its adsorption onto a cell membrane. This general kinetic model

  7. Kinetics of molybdenite oxidizing leaching in alkali medium by ozone

    International Nuclear Information System (INIS)

    Medvedev, A.S.; Sokratova, N.B.; Litman, I.V.; Zelikman, A.N.

    1985-01-01

    On the basis of investigation of the process kinetics proposed is a model of oxidizing leaching of molybdenite in alkali medium while ozonization of the solution by ozoneair mixture. A kinetic equation is derived, that describes experimental data satisfactorily

  8. A kinetics database and scripts for PHREEQC

    Science.gov (United States)

    Hu, B.; Zhang, Y.; Teng, Y.; Zhu, C.

    2017-12-01

    Kinetics of geochemical reactions has been increasingly used in numerical models to simulate coupled flow, mass transport, and chemical reactions. However, the kinetic data are scattered in the literature. To assemble a kinetic dataset for a modeling project is an intimidating task for most. In order to facilitate the application of kinetics in geochemical modeling, we assembled kinetics parameters into a database for the geochemical simulation program, PHREEQC (version 3.0). Kinetics data were collected from the literature. Our database includes kinetic data for over 70 minerals. The rate equations are also programmed into scripts with the Basic language. Using the new kinetic database, we simulated reaction path during the albite dissolution process using various rate equations in the literature. The simulation results with three different rate equations gave difference reaction paths at different time scale. Another application involves a coupled reactive transport model simulating the advancement of an acid plume in an acid mine drainage site associated with Bear Creek Uranium tailings pond. Geochemical reactions including calcite, gypsum, and illite were simulated with PHREEQC using the new kinetic database. The simulation results successfully demonstrated the utility of new kinetic database.

  9. A novel zeolite process for clean end use of hydrocarbon products

    Energy Technology Data Exchange (ETDEWEB)

    Keskinen, K M [Neste Oy, Porvoo (Finland). Technology Centre

    1997-12-31

    In recent years zeolites such as ZSM-5 have attracted considerable interest for the catalysis of a wide range of hydrocarbon transformations. A novel process developed by Neste converts light olefins to higher molecular weight hydrocarbon products. A wide range of high quality diesel, solvents and lube oils can be produced by the new NESKO process. Hydrotreated products have excellent properties; negligible sulphur or nitrogen compounds, very low aromatic content and pour point lower than -50 deg C. Proprietary technology is used in this olefin oligomerization process. (author) (7 refs.)

  10. A novel zeolite process for clean end use of hydrocarbon products

    Energy Technology Data Exchange (ETDEWEB)

    Keskinen, K.M. [Neste Oy, Porvoo (Finland). Technology Centre

    1996-12-31

    In recent years zeolites such as ZSM-5 have attracted considerable interest for the catalysis of a wide range of hydrocarbon transformations. A novel process developed by Neste converts light olefins to higher molecular weight hydrocarbon products. A wide range of high quality diesel, solvents and lube oils can be produced by the new NESKO process. Hydrotreated products have excellent properties; negligible sulphur or nitrogen compounds, very low aromatic content and pour point lower than -50 deg C. Proprietary technology is used in this olefin oligomerization process. (author) (7 refs.)

  11. Cesium removal and kinetics equilibrium: Precipitation kinetics

    International Nuclear Information System (INIS)

    Barnes, M.J.

    1999-01-01

    This task consisted of both non-radioactive and radioactive (tracer) tests examining the influence of potentially significant variables on cesium tetraphenylborate precipitation kinetics. The work investigated the time required to reach cesium decontamination and the conditions that affect the cesium precipitation kinetics

  12. Modeling composting kinetics: A review of approaches

    NARCIS (Netherlands)

    Hamelers, H.V.M.

    2004-01-01

    Composting kinetics modeling is necessary to design and operate composting facilities that comply with strict market demands and tight environmental legislation. Current composting kinetics modeling can be characterized as inductive, i.e. the data are the starting point of the modeling process and

  13. Kinetics of tetrataenite disordering

    International Nuclear Information System (INIS)

    Dos Santos, E.; Gattacceca, J.; Rochette, P.; Fillion, G.; Scorzelli, R.B.

    2015-01-01

    Tetrataenite is a chemically ordered L1 0 -type Fe 50 Ni 50 alloy detected for the first time in 1977 by 57 Fe Mössbauer spectroscopy studies in iron meteorites. The thermal history of meteorites, in particular short thermal events like those associated to hypervelocity impacts, can be constrained by tracing the presence of tetrataenite or its disordering into taenite. The knowledge of the disordering kinetics of tetrataenite, that is associated with changes in its magnetic properties, is still very fragmentary so that the time–temperature history of these meteorites cannot be constrained in details. Furthermore, knowledge of disordering kinetics is important due to potential technological application of tetrataenite as a rare-earth free strong magnet. Thus, this work provides the first time–temperature data for disordering reaction of tetrataenite. We have shown that disordering is not an instantaneous process but is a kinetic limited reaction. It was shown that disordering may take place at any temperature above the order–disorder transition for L 10 superstructure phase (∼320 °C) when the appropriate time-scale is considered. This result means that the apparent Curie point for tetrataenite is not an absolute property in the sense that any estimate of this parameter should be referred to a given time-scale. - Highlights: • The first time–temperature data for tetrataenite disordering reaction is provided. • Previous works does not give a complete picture of tetrataenite disordering. • Apparent Curie temperature of tetrataenite should be referred to a time-scale. • Tetrataenite can be used as a probe to detect thermal/shock events recorded in meteorites

  14. Plasma kinetic theory

    International Nuclear Information System (INIS)

    Elliott, J.A.

    1993-01-01

    Plasma kinetic theory is discussed and a comparison made with the kinetic theory of gases. The plasma is described by a modified set of fluid equations and it is shown how these fluid equations can be derived. (UK)

  15. Chemical kinetics and combustion modeling

    Energy Technology Data Exchange (ETDEWEB)

    Miller, J.A. [Sandia National Laboratories, Livermore, CA (United States)

    1993-12-01

    The goal of this program is to gain qualitative insight into how pollutants are formed in combustion systems and to develop quantitative mathematical models to predict their formation rates. The approach is an integrated one, combining low-pressure flame experiments, chemical kinetics modeling, theory, and kinetics experiments to gain as clear a picture as possible of the process in question. These efforts are focused on problems involved with the nitrogen chemistry of combustion systems and on the formation of soot and PAH in flames.

  16. Chapter 22. Cell population kinetics

    International Nuclear Information System (INIS)

    Tubiana, M.

    1975-01-01

    The main contribution of radioisotopes to the development of a new discipline, cell population kinetics, was shown. The aim of this science is to establish, for each tissue of the organism, the life span of its component cells and the mechanisms governing its growth, its differentiation and its homeostasis with respect to outside attacks. Labelling techniques have been used to follow the cells during these various processes. The case of non-dividing cells was considered first, taking as example, the red blood cells of which the lifetime was studied, after which the case of proliferating cells was examined using 14 C- or tritium-labelled thymidine. The methods used to measure the cell cycle parameters were described: labelled-mitosis curve method, double-labelling and continuous labelling methods, proliferation coefficient measurement. Cell kinetics were shown to allow an interpretation of radiobiological data. Finally the practical value of cell kinetics research was shown [fr

  17. Kinetic theory and transport phenomena

    CERN Document Server

    Soto, Rodrigo

    2016-01-01

    This textbook presents kinetic theory, which is a systematic approach to describing nonequilibrium systems. The text is balanced between the fundamental concepts of kinetic theory (irreversibility, transport processes, separation of time scales, conservations, coarse graining, distribution functions, etc.) and the results and predictions of the theory, where the relevant properties of different systems are computed. The book is organised in thematic chapters where different paradigmatic systems are studied. The specific features of these systems are described, building and analysing the appropriate kinetic equations. Specifically, the book considers the classical transport of charges, the dynamics of classical gases, Brownian motion, plasmas, and self-gravitating systems, quantum gases, the electronic transport in solids and, finally, semiconductors. Besides these systems that are studied in detail, concepts are applied to some modern examples including the quark–gluon plasma, the motion of bacterial suspen...

  18. Synthesis of Ag-Cu and Ag-Cu{sub 2}O alloy nanoparticles using a seed-mediated polyol process, thermodynamic and kinetic aspects

    Energy Technology Data Exchange (ETDEWEB)

    Niknafs, Yasaman; Amirjani, Amirmostafa; Marashi, Pirooz, E-mail: pmarashi@aut.ac.ir; Fatmehsari, Davoud Haghshenas

    2017-03-01

    In this paper, Ag, Ag-Cu and Ag-Cu{sub 2}O nanoparticles were synthesized using a modified polyol method. Size, shape and composition of the obtained nanostructures were effectively controlled by adjusting the kinetic and thermodynamic conditions. Response surface methodology was employed to consider the interaction of parameters and to develop a polynomial equation for predicting the size of the silver nanoparticles. The precisely controlled silver nanoaprticles were used as the seeds for the formation of alloyed nanoparticles. By manipulating the involved parameters, both spherical and cubical Ag-Cu and Ag-Cu{sub 2}O nanostructures are obtainable in the size range of 90–100 nm. The morphological, optical and compositional characteristics of the obtained nanostructures were studied using SEM, FE-SEM, UV–Vis, EDS and XRD. - Highlights: • Synthesis of Ag, Ag-Cu and Ag-Cu{sub 2}O alloy nanostructures. • RSM was successfully employed for predicting the size of the AgNPs. • Size and composition tuning by adjusting the kinetic and thermodynamic conditions.

  19. Thermodynamic and kinetic verification of tetra-n-butyl ammonium nitrate (TBANO3) as a promoter for the clathrate process applicable to precombustion carbon dioxide capture.

    Science.gov (United States)

    Babu, Ponnivalavan; Yao, Minghuang; Datta, Stuti; Kumar, Rajnish; Linga, Praveen

    2014-03-18

    In this study, tetra-n-butyl ammonium nitrate (TBANO3) is evaluated as a promoter for precombustion capture of CO2 via hydrate formation. New hydrate phase equilibrium data for fuel gas (CO2/H2) mixture in presence of TBANO3 of various concentrations of 0.5, 1.0, 2.0, 3.0, and 3.7 mol % was determined and presented. Heat of hydrate dissociation was calculated using Clausius-Clapeyron equation and as the concentration of TBANO3 increases, the heat of hydrate dissociation also increases. Kinetic performance of TBANO3 as a promoter at different concentrations was evaluated at 6.0 MPa and 274.2 K. Based on induction time, gas uptake, separation factor, hydrate phase CO2 composition, and rate of hydrate growth, 1.0 mol % TBANO3 solution was found to be the optimum concentration at the experimental conditions of 6.0 MPa and 274.2 K for gas hydrate formation. A 93.0 mol % CO2 rich stream can be produced with a gas uptake of 0.0132 mol of gas/mol of water after one stage of hydrate formation in the presence of 1.0 mol % TBANO3 solution. Solubility measurements and microscopic images of kinetic measurements provide further insights to understand the reason for 1.0 mol % TBANO3 to be the optimum concentration.

  20. Reaction mechanisms and kinetics of the elimination processes of 2-chloroethylsilane and derivatives: A DFT study using CTST, RRKM, and BET theories

    Science.gov (United States)

    Shiroudi, Abolfazl; Zahedi, Ehsan; Oliaey, Ahmad Reza; Deleuze, Michael S.

    2017-03-01

    The thermal decomposition kinetics of 2-chloroethylsilane and derivatives in the gas phase has been studied computationally using density functional theory, along with various exchange-correlation functionals (UM06-2x and ωB97XD) and the aug-cc-pVTZ basis set. The calculated energy profile has been supplemented with calculations of kinetic rate constants under atmospheric pressure and in the fall-off regime, using transition state theory (TST) and statistical Rice-Ramsperger-Kassel-Marcus (RRKM) theory. Activation energies and rate constants obtained using the UM06-2x/aug-cc-pVTZ approach are in good agreement with the experimental data. The decomposition of 2-chloroethyltriethylsilane species into the related products [C2H4 + Et3SiCl] is characterized by 6 successive structural stability domains associated to the sequence of catastrophes C8H19SiCl: 6-C†FCC†[FF]-0: C6H15SiCl + C2H4. Breaking of Si-C bonds and formation of Si-Cl bonds occur in the vicinity of the transition state.

  1. Production kinetics of zirconium tetrachloride

    International Nuclear Information System (INIS)

    Sudjoko, D.; Masduki, B.; Sunardjo; Sulistyo, B.

    1996-01-01

    This research was intended to study the kinetics of zirconium tetrachloride production. The process was carried out in semi continuous reactor, equipped with heater, temperature controller, sublimator and scrubber. The variables investigated were time, temperature and the pellet forming pressure. Within the range of variables studied, the expression of the process in the chemical reaction controller region and diffusion controller region were both presented. (author)

  2. Kinetics of UO2 sintering

    International Nuclear Information System (INIS)

    Ristic, M.M.

    1962-01-01

    Detailed conclusions related to the UO 2 sintering can be drawn from investigating the kinetics of the sintering process. This report gives an thorough analysis of the the data concerned with sintering available in the literature taking into account the Jander and Arrhenius laws. This analysis completes the study of influence of the O/U ratio and the atmosphere on the sintering. Results presented are fundamentals of future theoretical and experimental work related to characterisation of the UO 2 sintering process

  3. Kinetic theory of nonideal gases and nonideal plasmas

    CERN Document Server

    Klimontovich, Yu L

    2013-01-01

    Kinetic Theory of Nonideal Gases and Nonideal Plasmas presents the fundamental aspects of the kinetic theory of gases and plasmas. The book consists of three parts, which attempts to present some of the ideas, methods and applications in the study of the kinetic processes in nonideal gases and plasmas. The first part focuses on the classical kinetic theory of nonideal gases. The second part discusses the classical kinetic theory of fully ionized plasmas. The last part is devoted to the quantum kinetic theory of nonideal gases and plasmas. A concluding chapter is included, which presents a shor

  4. A low-energy intensive electrochemical system for the eradication of Escherichia coli from ballast water: Process development, disinfection chemistry, and kinetics modeling

    International Nuclear Information System (INIS)

    Nadeeshani Nanayakkara, K.G.; Khorshed Alam, A.K.M.; Zheng Yuming; Paul Chen, J.

    2012-01-01

    The invasion of biological organisms via ballast water has created threats to the environment and human health. In this study, a cost-effective electrochemical disinfection reactor was developed to inactivate Escherichia coli, one of the IMO-regulated indicator microbes, in simulated ballast water. The complete inactivation of E. coli could be achieved within a very short time (150, 120, or 60 s) with an energy consumption as low as 0.0090, 0.0074 or 0.0035 kWh/m 3 for ballast water containing E. coli at concentrations of 10 8 , 10 7 and 10 6 CFU/100 mL, respectively. Electrochemical chlorination was the major disinfection mechanism in chloride-abundant electrolytes, whereas oxidants such as ozone and free radicals contributed to 20% of the disinfection efficiency in chloride-free electrolytes. Moreover, a disinfection kinetics model was successfully developed to describe the inactivation of E. coli.

  5. Kinetics, mass transport characteristics, and structural changes during air-drying of purple yam (Dioscorea Alata L.) at different process conditions

    Science.gov (United States)

    De Vera, Flordeliza C.; Comaling, Leif Anthony B.; Lao, Iya Ray Alyanna M.; Caparanga, Alvin R.; Sauli, Zaliman

    2017-11-01

    This experiment was designed to follow the 2k factorial design to study the effects of the three drying parameters on the drying characteristics and effective moisture diffusivity and to fit each run performed on the best thin-layer drying kinetics model. Raw purple yam samples were pre-treated and undergone the designed drying procedures at which the weight of the samples were recorded every minute until such time that the sample weights become constant. Scanning Electron Microscopy (SEM) is utilized for qualitative analysis of the dried samples. The number of pores per unit area and the overall aesthetics of the surface of the dried samples were compared also using SEM. Considering the qualitative analysis conducted on the samples from the images of SEM, dried samples from run 2 has the most desirable conditions such as high temperature and low air velocity for drying because the samples from this run have large pore diameters with minimal cell breakages.

  6. Hydroxylamine derivatives in the Purex Process Part VII. The redox reactive kinetics and mechanism of dimethylhydroxylamine and vanadium(V) in nitric medium

    International Nuclear Information System (INIS)

    Anyun Zhang; Institute of Research and Innovation, Chiba; Guoping Xiao; Chinese Inst. of Atomic Energy, Beijing; Jingxin Hu; Hui He

    2003-01-01

    The kinetics of the redox reaction between dimethylhydroxylamine (DMH) and vanadium(V) in nitric acid has been studied by spectrophotometry at 23.1 deg C. The rate equation of the reaction is determined as -d[V(V)]/dt=k[V(V)][DMH] by investigating the influence of the concentrations of V(V) and DMH, acidity, ionic strength and the ratio of the initial concentrations of reactants on the redox reaction. The rate constant of the reaction k = 9.95 ± 0.52 (mol/l) -1 x s -1 when the ionic strength is 1.00 mol/l. The activation energy of the reaction is 22.1 kJ/mol. A possible mechanism of the redox reaction has been suggested on the basis of an electron spin resonance(ESR) spectrum of dimethyl nitroxyl radical, (CH 3 ) 2 NO. (author)

  7. Electrochemical degradation of PAH compounds in process water: A kinetic study on model solutions and a proof of concept study on runoff water from harbour sediment purification

    DEFF Research Database (Denmark)

    Muff, Jens; Søgaard, Erik Gydesen

    2010-01-01

    The present study has investigated the possibility to apply electrochemical oxidation in the treatment of polycyclic aromatic hydrocarbon (PAHs) pollutants in water. The reaction kinetics of naphthalene, fluoranthene, and pyrene oxidation have been studied in a batch recirculation experimental...... oxidation side reaction at lower applied voltages. A proof of concept study in real polluted water demonstrated the applicability of the electrochemical oxidation technique for larger scale use, where especially the indirect chloride mediated oxidation approach was a promising technique. However, the risk....... Decreased current densities from 200 to 15 mA cm-2 in the NaCl electrolyte also decreased the removal rates, but significantly enhanced the current efficiencies of the PAH oxidation, based on a defined current efficiency constant, kq. This observation is believed to be due to the suppression of the water...

  8. A 3D kinetic Monte Carlo simulation study of resistive switching processes in Ni/HfO2/Si-n+-based RRAMs

    International Nuclear Information System (INIS)

    Aldana, S; García-Fernández, P; Jiménez-Molinos, F; Gómez-Campos, F; Roldán, J B; Rodríguez-Fernández, Alberto; Romero-Zaliz, R; González, M B; Campabadal, F

    2017-01-01

    A new RRAM simulation tool based on a 3D kinetic Monte Carlo algorithm has been implemented. The redox reactions and migration of cations are developed taking into consideration the temperature and electric potential 3D distributions within the device dielectric at each simulation time step. The filamentary conduction has been described by obtaining the percolation paths formed by metallic atoms. Ni/HfO 2 /Si-n + unipolar devices have been fabricated and measured. The different experimental characteristics of the devices under study have been reproduced with accuracy by means of simulations. The main physical variables can be extracted at any simulation time to clarify the physics behind resistive switching; in particular, the final conductive filament shape can be studied in detail. (paper)

  9. The temperature hydration kinetics

    Directory of Open Access Journals (Sweden)

    Mircea Oroian

    2017-07-01

    Full Text Available The aim of this study is to evaluate the hydration kinetics of lentil seeds (Lens culinaris in water at different temperatures (25, 32.5, 40, 55, 70 and 80 °C for assessing the adequacy of models for describing the absorption phenomena during soaking. The diffusion coefficient values were calculated using Fick’s model for spherical and hemispherical geometries and the values were in the range of 10−6 m2/s. The experimental data were fitted to Peleg, Sigmoidal, Weibull and Exponential models. The models adequacy was determined using regression coefficients (R2, root mean square error (RMSE and reduced chi-square (χ2. The Peleg model is the suitable one for predicting the experimental data. Temperature had a positive and significant effect on the water absorption capacities and absorption was an endothermic process.

  10. NUMERICAL EVALUATION OF THE EFFECTS OF SOFT-MELTING PROPERTIES ON THE KINETIC OF (CAFE2 O4 -CA2 FE2 O5 FORMATION IN THE IRON ORE SINTERING PROCESS

    Directory of Open Access Journals (Sweden)

    José Adilson de Castro

    2013-03-01

    Full Text Available This paper presents a mathematical model able to predict the influence of soft-melting properties of the blend of raw materials used in the iron ore sintering process in the kinetic formation of calcium ferrite and di-calcium ferrite constituents. The model is based on the simultaneous solution of transport equations of Momentum, energy and chemical species in multiphase multicomponent systems coupled with the chemical reactions kinetics and phase transformations that occur within the sinter bed. The numerical solution is obtained using the finite volume method and the model is validated using monitoring data from an industrial scale sintering plant. After validation, the model was used to predict processing conditions using raw materials with different soft-melting properties. Results indicate that the temperatures of starting soft-melting, shrinkage and melting range are the main parameters to be controlled in order to attain liquid phases formation responsible to confer good mechanical and reducibility properties for the sinter product. In this study was found that raw materials with high soft-melting temperature and wilder temperature of mushy zone could decrease up to 30% the calcium ferrites formation and hence deteriorates the metallurgical properties of the sinter.

  11. Chemical kinetics: on the heterogeneous catalysis processes leading to an exchange between two phases. Example: isotopic exchange reactions; Cinetique chimique: sur les processus de catalyse 'heterogene' conduisant a un echange entre deux phases. Exemple: reactions d'echange isotopique

    Energy Technology Data Exchange (ETDEWEB)

    Dirian, G; Grandcollot, P [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires

    1961-07-01

    For an exchange reaction between a gaseous and a liquid phase proceeding by 'heterogeneous' catalysis in the liquid phase, diffusion in the liquid and the chemical reaction are two simultaneous and indivisible processes. We have nevertheless been able to establish criteria making it possible to distinguish between a really homogeneous kinetic process and a pseudo-homogeneous one. (author) [French] Pour une reaction d'echange entre une phase gazeuse et une phase liquide procedant par catalyse 'heterogene' en phase liquide, la diffusion dans le liquide et la reaction chimique sont deux etapes simultanees et indissociables. Nous avons pu neanmoins etablir des criteres permettant de distinguer entre une cinetique homogene vraie et une cinetique pseudo-homogene. (auteur)

  12. Kinetic advantage of controlled intermediate nuclear fusion

    International Nuclear Information System (INIS)

    Guo Xiaoming

    2012-01-01

    The dominated process of controlled fusion is to let nuclei gain enough kinetic energy to overcome Coulomb barrier. As a result, a fusion scheme can consider two factors in its design: to increase kinetic energy of nuclei and to alter the Coulomb barrier. Cold Fusion and Hot fusion are all one-factor schemes while Intermediate Fusion is a twofactors scheme. This made CINF kinetically superior. Cold Fusion reduces deuteron-deuteron distance, addressing Coulomb barrier, and Hot Fusion heat up plasma into extreme high temperature, addressing kinetic energy. Without enough kinetic energy made Cold Fusion skeptical. Extreme high temperature made Hot Fusion very difficult to engineer. Because CIFN addresses both factors, CIFN is a more promising technique to be industrialized.

  13. Statistical optimization for enhanced yields of probiotic Bacillus coagulans and its phage resistant mutants followed by kinetic modelling of the process.

    Science.gov (United States)

    Pandey, Kavita R; Joshi, Chetan; Vakil, Babu V

    2016-01-01

    Probiotics are microorganisms which when administered in adequate amounts confer health benefits to the host. A leading pharmaceutical company producing Bacillus coagulans as a probiotic was facing the problem of recurring phage attacks. Two mutants viz. B. co PIII and B. co MIII that were isolated as phage resistant mutants after UV irradiation and MMS treatment of phage sensitive B. coagulans parental culture were characterized at functional and molecular level and were noted to have undergone interesting genetic changes. The non-specific genetic alterations induced by mutagenesis can also lead to alterations in cell performance. Hence, in the current study the parental strain and the two mutants were selected for shake flask optimization. Plackett-Burman design was used to select the significant culture variables affecting biomass production. Evolutionary operation method was applied for further optimization. The study showed wide variations in the nutritional requirements of phage resistant mutants, post exposure to mutagens. An increment of 150, 134 and 152 % was observed in the biomass productions of B. coagulans (parental type) and mutants B.co PIII and B.co MIII respectively, compared to the yield from one-factor-at-a-time technique. Using Logistic and modified Leudeking-Piret equations, biomass accumulation and substrate utilization efficiency of the bioprocess were determined. The experimental data was in agreement with the results predicted by statistical analysis and modelling. The developed model may be useful for controlling the growth and substrate consumption kinetics in large scale fermentation using B. coagulans .

  14. Collection and processing of information in biological kinetics studies with radioactive tracers; Collecte et traitement de l'information dans les etudes de cinetique biologique avec traceurs radioactifs

    Energy Technology Data Exchange (ETDEWEB)

    Remy, J; Lafuma, J [Commissariat a l' Energie Atomique, Fontenay-aux-Roses (France). Centre d' Etudes Nucleaires

    1968-07-01

    The authors present an automatic method for the collection and treatment of information in biological kinetics experiments using radioactive tracers. The recording are made without any time constant on magnetic tape. The information recorded is sampled by a 400 channel multi-scale analyzer and transferred to punched cards. The digital analysis is done by an I.B.M. computer. The method is illustrated by an example: the hepatic fixation of colloidal gold in the pig. Its advantages and requirements are discussed. In the appendix are given the FORTRAN texts for two programmes used in treating the example presented. (authors) [French] Les auteurs presentent une methode automatique de collecte et de traitement de l'information dans les experiences de cinetique biologique utilisant les traceurs radioactifs. Les enregistrements sont realises sans constante de temps sur bande magnetique. L'information enregistree fait l'objet d'un echantillonnage a l'aide d'un analyseur a 400 canaux en mode multi-echelle puis est transferee sur cartes perforees. L'exploitation digitale est confiee a un ordinateur I.B.M.. La methode est illustree par un exemple d'etude de la fixation hepatique de l'or colloidal chez le porc. Ses avantages et ses exigences sont discutes. En annexe figurent les textes en FORTRAN de deux programmes utilises pour le traitement de l'exemple cite. (auteurs)

  15. Principles of chemical kinetics

    CERN Document Server

    House, James E

    2007-01-01

    James House's revised Principles of Chemical Kinetics provides a clear and logical description of chemical kinetics in a manner unlike any other book of its kind. Clearly written with detailed derivations, the text allows students to move rapidly from theoretical concepts of rates of reaction to concrete applications. Unlike other texts, House presents a balanced treatment of kinetic reactions in gas, solution, and solid states. The entire text has been revised and includes many new sections and an additional chapter on applications of kinetics. The topics covered include quantitative rela

  16. Introduction to chemical kinetics

    CERN Document Server

    Soustelle, Michel

    2013-01-01

    This book is a progressive presentation of kinetics of the chemical reactions. It provides complete coverage of the domain of chemical kinetics, which is necessary for the various future users in the fields of Chemistry, Physical Chemistry, Materials Science, Chemical Engineering, Macromolecular Chemistry and Combustion. It will help them to understand the most sophisticated knowledge of their future job area. Over 15 chapters, this book present the fundamentals of chemical kinetics, its relations with reaction mechanisms and kinetic properties. Two chapters are then devoted to experimental re

  17. Reduced Chemical Kinetic Mechanisms for JP-8 Combustion

    National Research Council Canada - National Science Library

    Montgomery, Christopher J; Cannon, S. M; Mawid, M. A; Sekar, B

    2002-01-01

    Using CARM (Computer Aided Reduction Method), a computer program that automates the mechanism reduction process, six different reduced chemical kinetic mechanisms for JP-8 combustion have been generated...

  18. Kinetic Modeling of Vacuum Gas Oil Hydrotreatment using a Molecular Reconstruction Approach Modélisation cinétique de l’hydrotraitement de distillats sous vide utilisant une approche de reconstruction moléculaire

    Directory of Open Access Journals (Sweden)

    Charon-Revellin N.

    2010-10-01

    Full Text Available Vacuum Gas Oils (VGO are heavy petroleum cuts (boiling points ranging from 350 to 550 ˚C that can be transformed into valuable fuels (gasolines, diesels by fluid catalytic cracking or hydrocracking. Prior to these conversion processes, hydrotreating is required in order to eliminate the impurities in VGOs. The hydrotreatment process enables to meet the environmental specifications (total sulfur contents and to prevent nitrogen poisoning of conversion catalysts. In order to develop a kinetic model based on an accurate VGOs molecular description, innovative analytical tools and molecular reconstruction techniques were used in this work. A lumped model using a Langmuir-Hinshelwood representation was developed for hydrodearomatization, hydrodesulfurization and hydrodenitrogenation of the VGO. This lumped model was successfully applied to the experimental feed pretreatment data and was able to predict evolution of concentration of the aromatics, nitrogen and sulfur species. Les Distillats Sous Vide (DSV sont des coupes pétrolières lourdes (gamme de températures d'ébullition 350 à 550 °C qui peuvent être valorisées en carburants (essence, gazole par craquage catalytique ou par hydrocraquage. Un hydrotraitement est requis avant ces procédés de conversion afin d'éliminer les impuretés du DSV. De cette manière, le procédé d'hydrotraitement permet d'attendre les spécifications environnementales (teneur en soufre ainsi que de prévenir l'empoisonnement par les composés azotés des catalyseurs de conversion. De manière à pouvoir développer un modèle cinétique basé sur une description moléculaire précise des DSV, des outils analytiques innovant et des techniques de reconstruction moléculaire ont été utilisés dans ce travail. Un modèle cinétique de regroupement utilisant une représentation de type Langmuir-Hinshelwood a été développé pour l'hydrodésaromatisation, l'hydrodésulfuration et l'hydrodésazotation des DSV. Ce

  19. Kinetic equation solution by inverse kinetic method

    International Nuclear Information System (INIS)

    Salas, G.

    1983-01-01

    We propose a computer program (CAMU) which permits to solve the inverse kinetic equation. The CAMU code is written in HPL language for a HP 982 A microcomputer with a peripheral interface HP 9876 A ''thermal graphic printer''. The CAMU code solves the inverse kinetic equation by taking as data entry the output of the ionization chambers and integrating the equation with the help of the Simpson method. With this program we calculate the evolution of the reactivity in time for a given disturbance

  20. Kinetic and Modeling Investigation to Provide Design Guidelines for the NREL Dilute-Acid Process Aimed at Total Hydrolysis/Fractionation of Lignocellulosic Biomass: July 1998

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Y. Y.; Iyer, P.; Xiang, Q.; Hayes, J.

    2004-08-01

    Following up on previous work, subcontractor investigated three aspects of using NREL ''pretreatment'' technology for total hydrolysis (cellulose as well as hemicellulose) of biomass. Whereas historic hydrolysis of biomass used either dilute acid or concentrated acid technology for hydrolysis of both hemicellulose and cellulose, NREL has been pursuing very dilute acid hydrolysis of hemicellulose followed by enzymatic hydrolysis of cellulose. NREL's countercurrent shrinking-bed reactor design for hemicellulose hydrolysis (pretreatment) has, however, shown promise for total hydrolysis. For the first task, subcontractor developed a mathematical model of the countercurrent shrinking bed reactor operation and, using yellow poplar sawdust as a feedstock, analyzed the effect of: initial solid feeding rate, temperature, acid concentration, acid flow rate, Peclet number (a measure of backmixing in liquid flow), and bed shrinking. For the second task, subcontractor used laboratory trials, with yellow poplar sawdust and 0.07 wt% sulfuric acid at various temperatures, to verify the hydrolysis of cellulose to glucose (desired) and decomposition of glucose (undesired) and determine appropriate parameters for use in kinetic models. Unlike cellulose and hemicellulose, lignins, the third major component of biomass, are not carbohydrates that can be broken down into component sugars. They are, however, aromatic complex amorphous phenolic polymers that can likely be converted into low-molecular weight compounds suitable for production of fuels and chemicals. Oxidative degradation is one pathway for such conversion and hydrogen peroxide would be an attractive reagent for this, as it would leave no residuals. For the third task, subcontractor reacted lignin with hydrogen peroxide under various conditions and analyzed the resulting product mix.