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Sample records for solvolysis

  1. Report for fiscal 1981 of Sunshine Program coal group. Basic research on Solvolysis liquefaction technology; 1981 nendo solvolysis ekika gijutsu no kiso kenkyu hokokusho

    NONE

    1982-03-01

    Basic research is conducted on the Solvolysis liquefaction process for the purpose of producing from coal an ashless, low-sulfur, pollution-free liquid fuel. In the research on the Solvolysis liquefaction (1st stage liquefaction) of coal using a hydrogenation solvent, the Solvolysis liquefaction of coal is studied, for which a refined Solvolysis pitch containing coal substances and a hydride of solvent refined coal are used as Solvolysis liquefaction solvents for the 1st stage. In the research on the 1st stage liquefaction reaction conditions using a high-temperature closed process, two methods are employed. One is a method that uses a mini-pump type reactor in which a small hermetic container is submerged in a high-temperature solvent for rapid heating and the other is a method that uses a pipe type reactor in which coal slurry is caused to travel through a pipe heated to a high temperature. For the analysis of the 2nd stage liquefaction (hydrogenation) reaction conditions, the properties of the 2nd coal liquid, and the constitution of the 2nd coal liquid, and the for the research on the 1st stage liquefaction capacity, the hydrogenation of anthracene oil and solvent refined coal as recyclable solvent models is studied. (NEDO)

  2. FY 1980 Report on results of Sunshine Project by Coal Group. Basic researches on coal liquefaction techniques by solvolysis; 1980 nendo sunshine keikaku sekitanhan hokokusho. Sekitan no solvolysis ekika gijutsu no kiso kenkyu

    NONE

    1981-07-01

    The basic experimental researches were carried out for coal liquefaction by solvolysis. The studied items include hydrogenation conditions for treating the primary liquefied products, asphalt, pitch and model solvents (e.g., anthracene oil) in the presence of a commercial catalyst, solvolysis conditions for finely divided, molten coal using a hydrogenation recycled solvent, hydrotreating solvents, analysis of solvolysis-liquefied products, and liquefaction capacity of fractionated solvents for finely divided, molten coal. The studied items for separation of minerals include settlement at high temperature of the solid residue from the first liquefaction stage, and changed coal particle size distribution as a result of the first-stage liquefaction reactions in the presence of a hydrogenation solvent. The experimental study results indicate that conversion of finely divided molten coal into asphaltenes and preasphaltenes is notably accelerated in the phase-II coal liquefaction process by solvolysis, when a hydrotreating solvent is used for the first stage solvolysis process. (NEDO)

  3. Solvent consumption in non-catalytic alcohol solvolysis of biorefinery lignin

    Nielsen, J. B.; Jensen, A.; Schandel, Christian Bækhøj

    2017-01-01

    Lignin solvolysis in supercritical alcohols provides a method for producing a deoxygenated liquid bio-oil. Solvent consumption is however inevitable and due to the high cost of alcohols, relative to a bio-oil product, it can hinder commercial viability. In order to investigate the reactions...... of solvent consumption we studied solvolysis of biorefinery lignin in several primary alcohols. Lignin solvolysis in methanol, ethanol, 1-propanol and 1-butanol performed similarly with respect to bio-oil composition; however, methanol gave much lower bio-oil yield. Solvent consumption increases...... with reaction temperature for all alcohols and from 10 wt% at 300 °C to 35 wt% at 400 °C when using ethanol. The mechanism for solvent consumption was found mainly to take place through three different reactions: direct decomposition to gas through decarbonylation, formation of light condensation products...

  4. Correlation of the Rates of Solvolysis of Neopentyl Chloroformate—A Recommended Protecting Agent

    D’Souza, Malcolm J.; Carter, Shannon E.; Kevill, Dennis N.

    2011-01-01

    The specific rates of solvolysis of neopentyl chloroformate (1) have been determined in 21 pure and binary solvents at 45.0 °C. In most solvents the values are essentially identical to those for ethyl and n-propyl chloroformates. However, in aqueous-1,1,1,3,3,3-hexafluoro-2-propanol mixtures (HFIP) rich in fluoroalcohol, 1 solvolyses appreciably faster than the other two substrates. Linear free energy relationship (LFER) comparison of the specific rates of solvolysis of 1 with those for pheny...

  5. Correlation of the Rates of Solvolysis of Neopentyl Chloroformate—A Recommended Protecting Agent

    D’Souza, Malcolm J.; Carter, Shannon E.; Kevill, Dennis N.

    2011-01-01

    The specific rates of solvolysis of neopentyl chloroformate (1) have been determined in 21 pure and binary solvents at 45.0 °C. In most solvents the values are essentially identical to those for ethyl and n-propyl chloroformates. However, in aqueous-1,1,1,3,3,3-hexafluoro-2-propanol mixtures (HFIP) rich in fluoroalcohol, 1 solvolyses appreciably faster than the other two substrates. Linear free energy relationship (LFER) comparison of the specific rates of solvolysis of 1 with those for phenyl chloroformate and those for n-propyl chloroformate are helpful in the mechanistic considerations, as is also the treatment in terms of the Extended Grunwald-Winstein equation. It is proposed that the faster reaction for 1 in HFIP rich solvents is due to the influence of a 1,2-methyl shift, leading to a tertiary alkyl cation, outweighing the only weak nucleophilic solvation of the cation possible in these low nucleophilicity solvents. PMID:21541050

  6. Correlation of the rates of solvolysis of neopentyl chloroformate-a recommended protecting agent.

    D'Souza, Malcolm J; Carter, Shannon E; Kevill, Dennis N

    2011-02-15

    The specific rates of solvolysis of neopentyl chloroformate (1) have been determined in 21 pure and binary solvents at 45.0 °C. In most solvents the values are essentially identical to those for ethyl and n-propyl chloroformates. However, in aqueous-1,1,1,3,3,3-hexafluoro-2-propanol mixtures (HFIP) rich in fluoroalcohol, 1 solvolyses appreciably faster than the other two substrates. Linear free energy relationship (LFER) comparison of the specific rates of solvolysis of 1 with those for phenyl chloroformate and those for n-propyl chloroformate are helpful in the mechanistic considerations, as is also the treatment in terms of the Extended Grunwald-Winstein equation. It is proposed that the faster reaction for 1 in HFIP rich solvents is due to the influence of a 1,2-methyl shift, leading to a tertiary alkyl cation, outweighing the only weak nucleophilic solvation of the cation possible in these low nucleophilicity solvents.

  7. Comparative environmental and human health evaluations of thermolysis and solvolysis recycling technologies of carbon fiber reinforced polymer waste.

    Khalil, Y F

    2018-06-01

    This quantitative research aims to compare environmental and human health impacts associated with two recycling technologies of CFRP waste. The 'baseline' recycling technology is the conventional thermolysis process via pyrolysis and the 'alternative' recycling technology is an emerging chemical treatment via solvolysis using supercritical water (SCW) to digest the thermoset matrix. Two Gate-to-Gate recycling models are developed using GaBi LCA platform. The selected functional unit (FU) is 1 kg CFRP waste and the geographical boundary of this comparative LCIA is defined to be within the U.S. The results of this comparative assessment brought to light new insights about the environmental and human health impacts of CFRP waste recycling via solvolysis using SCW and, therefore, helped close a gap in the current state of knowledge about sustainability of SCW-based solvolysis as compared to pyrolysis. Two research questions are posed to identify whether solvolysis recycling offers more environmental and human health gains relative to the conventional pyrolysis recycling. These research questions lay the basis for formulating two null hypotheses (H 0,1 and H 0,2 ) and their associated research hypotheses (H 1,1 and H 1,2 ). LCIA results interpretation included 'base case' scenarios, 'sensitivity studies,' and 'scenarios analysis.' The results revealed that: (a) recycling via solvolysis using SCW exhibits no gains in environmental and human health impacts relative to those impacts associated with recycling via pyrolysis and (b) use of natural gas in lieu of electricity for pyrolyzer's heating reduces the environmental and human health impacts by 37% (lowest) and up to 95.7% (highest). It is recommended that on-going experimental efforts that focus only on identifying the best solvent for solvolysis-based recycling should also consider quantification of the energy intensity as well as environmental and human health impacts of the proposed solvents. Copyright © 2018

  8. Report on 1979 result of Sunshine Project (detailed design). Part 1. Forty t/day solvolysis coal liquefaction pilot plant; 1979 nendo 40T/nichi solvolysis sekitan pilot plant shosai sekkei. 1

    NONE

    1980-03-01

    The subject design documents are the compilation of the result of the design operation for the 'detailed design of 40 t/day class solvolysis coal liquefaction pilot plant'. The design of this pilot plant was conducted using, as the fundamental reference, the basic data provided by Kyushu National Industrial Research Institute and Kyushu University and the results of a contract research on '1 t/day class solvolysis coal liquefaction plant'. The subject detailed design was intended for Phase 1 centering on a single stage liquefaction - coal liquefaction (transformation into pitch) by solvolysis liquefaction reaction. The areas covered consists of the pre-treatment process, material mixing process, reaction process, reaction freezing process, coke separation process, SR recovery process, pitch refining process, utility facilities, and waste water treatment facilities. Incidentally, the processes for which the design operation has been completed this year, particularly the reaction process, coke separation process, SR recovery process, etc., are in the field untrodden technologically in the world; therefore, their design method is supposed to be established from the results of the R and D on coal liquefaction, '1 t/day class solvolysis coal liquefaction plant.' (NEDO)

  9. Report on 1979 result of Sunshine Project (detailed design). Part 1. Forty t/day solvolysis coal liquefaction pilot plant; 1979 nendo 40T/nichi solvolysis sekitan pilot plant shosai sekkei. 1

    NONE

    1980-03-01

    The subject design documents are the compilation of the result of the design operation for the 'detailed design of 40 t/day class solvolysis coal liquefaction pilot plant'. The design of this pilot plant was conducted using, as the fundamental reference, the basic data provided by Kyushu National Industrial Research Institute and Kyushu University and the results of a contract research on '1 t/day class solvolysis coal liquefaction plant'. The subject detailed design was intended for Phase 1 centering on a single stage liquefaction - coal liquefaction (transformation into pitch) by solvolysis liquefaction reaction. The areas covered consists of the pre-treatment process, material mixing process, reaction process, reaction freezing process, coke separation process, SR recovery process, pitch refining process, utility facilities, and waste water treatment facilities. Incidentally, the processes for which the design operation has been completed this year, particularly the reaction process, coke separation process, SR recovery process, etc., are in the field untrodden technologically in the world; therefore, their design method is supposed to be established from the results of the R and D on coal liquefaction, '1 t/day class solvolysis coal liquefaction plant.' (NEDO)

  10. Report on the achievements in research and development of a coal liquefaction technology in the Sunshine Project in fiscal 1981. Development of a solvolysis liquefaction plant (research on realization of solvolysis pitch hydrogenation equipment); Sekitan ekika gijutsu no kenkyu kaihatsu, solvolysis ekika plant no kaihatsu seika hokokusho. Solvolysis pitch no suiten sochika kenkyu

    NONE

    1982-03-01

    Among researches on solvolysis coal liquefaction technologies in the Sunshine Project in fiscal 1981, this paper describes the research on realization of solvolysis pitch hydrogenation equipment. In realizing a hydrogenation and decomposition reacting equipment for the second stage reaction process, it is important to stabilize operation by preventing coking and catalytic deterioration in elevated temperature zones. Therefore, a reactor of catalytic fluid system was assumed. Fiscal 1981 has fabricated and experimented a flow testing equipment for the purpose of acquiring data for realization of the equipment. A reactor that can deal with temperatures higher than 400 degrees C was installed in a 0.1-t/d continuously operating equipment. For selecting adequate operating conditions, an operation manual was prepared from the results of the cold model test and the fundamental test on hydrogenation and decomposition. The devices used were verified to have good operability. As the gasification rate increases when the reaction temperature is raised, resulting in reduced oil yield, it is necessary to keep the temperature lower than 430 degrees C. Increased pressure does not increase the oil yield as much as it increases hydrogen consumption, hence pressure of 200 kg/cm{sup 2} or lower is suitable. The secondary hydrogenation solvent requires no proton donation performance, and light fraction should be preferable. Catalysts were also discussed, and a clue to improvements was obtained. (NEDO)

  11. Correlation of the Rates of Solvolysis of Neopentyl Chloroformate—A Recommended Protecting Agent

    Dennis N. Kevill

    2011-02-01

    Full Text Available The specific rates of solvolysis of neopentyl chloroformate (1 have been determined in 21 pure and binary solvents at 45.0 °C. In most solvents the values are essentially identical to those for ethyl and n-propyl chloroformates. However, in aqueous-1,1,1,3,3,3-hexafluoro-2-propanol mixtures (HFIP rich in fluoroalcohol, 1 solvolyses appreciably faster than the other two substrates. Linear free energy relationship (LFER comparison of the specific rates of solvolysis of 1 with those for phenyl chloroformate and those for n-propyl chloroformate are helpful in the mechanistic considerations, as is also the treatment in terms of the Extended Grunwald-Winstein equation. It is proposed that the faster reaction for 1 in HFIP rich solvents is due to the influence of a 1,2-methyl shift, leading to a tertiary alkyl cation, outweighing the only weak nucleophilic solvation of the cation possible in these low nucleophilicity solvents.

  12. Medium effects on a C-H bond fission reaction. Solvent and salt effects on the solvolysis of arylsulfonylmethyl perchlorates.

    Menninga, Lubbertus

    1976-01-01

    In this thesis, medium effects on the general basecatelyzed solvolysis of two arylsulfonylmethyl perchlorates are described and analyzed in some detail. For the aqueous media, special attention is given to possible effects due to changes in diffusionally averaged water structure. ... Zie: Summary

  13. Polymer Concentration-Controlled Substrate Specificity in Solvolysis of p-Nitrophenyl Alkanoates Catalyzed by 4-(Dialkylamino)pyridine- Functionalized Polymer in Aqueous Methanol Solution

    Wang, Guang-Jia

    1996-01-01

    The substrate specificity in solvolysis reactions of p-nitrophenyl alkanoates 2 (n=2-18) catalyzed by 4-(dialkylamino)pyridine-functionalized polymer 1 can be controlled by the concentration of 1 in 1...

  14. Nano Transition Metal Sulfide Catalyst for Solvolysis Liquefaction of Soda Lignin

    Fei-Ling, P.; Chin-Hua, C.; Sarani Zakaria; Soon-Keong, N.; Tze-Khong, L.

    2011-01-01

    Solvolysis liquefaction of soda lignin in the presence of various transition metal sulfide catalysts was studied to investigate the catalyst effects on the oil and gas yields, conversion rate and higher heating value (HHV) of oil. Nano sized copper sulfide, iron sulfide and molybdenum sulfide were successfully synthesized via a simple hydrothermal method under reaction temperature 200 degree Celsius for 90 min. The addition of transition metal sulfide based catalysts (CuS, MoS 2 and FeS 2 ) enhanced both production of the oils and gas and the higher heating value (HHV) of oil products. A high oil and gas yields of 82.1 % and 2890 cm 3 was obtained with MoS 2 at 250 degree Celsius for 60 min. Elemental analyses for the oils revealed that the liquid products have much higher heating values than the crude soda lignin powder. (author)

  15. Thermal properties of biopolyol from oil palm fruit fibre (OPFF) using solvolysis liquefaction technique

    Kormin, Shaharuddin; Rus, Anika Zafiah M.; Azahari, M. Shafiq M.

    2017-09-01

    Liquefaction is known to be an effective method for converting biomass into a biopolyol. The biomass liquefaction of oil palm fruit waste (PFW) in the presence of liquefaction solvent/polyhydric alcohol (PA): polyethylene glycol 400 (PEG400) using sulfuric acid as catalyst was studied. For all experiments, the liquefaction was conducted at 150°C and atmospheric pressure. The mass ratio of OPFW to liquefaction solvents used in all the experiments was, 1/3. Thermogravimetric analyses (TGA) were used to analyze their biopolyol and residue behaviors. It was found that thermal stability of oil palm mesocarp fibre (PM), oil palm shell (PS) and oil palm kernel (PK) fibre exhibited the first degradation of hard segment at (232, 104, 230°C) and the second degradation of soft segment at (314, 226, 412°C) as compared to PM, PS and PK residue which (229, 102, 227°C) of hard segment and (310, 219, 299°C) of segment, respectively. This behavior of thermal degradation of the hard segment and soft segment of biopolyol was changes after undergo solvolysis liquefaction process. The result analysis showed that the resulting biopolyol and its residue was suitable monomer for polyurethane (PU) synthesis for the production of PU foams.

  16. Report on the achievements in research and development of a coal liquefaction technology in the Sunshine Project in fiscal 1981. Development of a solvolysis liquefaction plant (development of a 1 t/d experimental plant and research on solvolysis liquefaction process); Sekitan ekika gijutsu no kenkyu kaihatsu, solvolysis ekika plant no kaihatsu seika hokokusho. 1t/nichi jikken plant no kaihatsu (solvolysis ekika process no kenkyu)

    NONE

    1982-03-01

    This paper describes the achievements in the Sunshine Project in fiscal 1981 in development of a solvolysis liquefaction plant. The solvolysis process is characterized by performing the first stage reaction (liquefaction) in a short time by using hydrogenated heavy solvent produced spontaneously in the process. This short-time liquefaction reaction was carried out continuously by using a 1-t/d experimental plant, and a prospect was obtained on smooth operation and realization of the device. A test using a testing device allowing the temperature to rise within several minutes was performed on the effectiveness of a hydrogenated coal based heavy solvent (fractions of a hydrogenated heavy anthracene as a model) as a study on the first stage reaction. Partially hydrogenated materials of polycyclic condensed aromatics in the heavy solvent is largely involved in the initial reaction. In the solid-liquid separation, solids and heavy fractions are selected and removed from the first stage reaction products, and the light fraction is supplied into the second stage reaction (hydrogenation). The solvent deliming process was tested by using a batch type solid-liquid separator, whose effectiveness was verified. Studies were performed by using Australian sub-bituminous coal on operation of a continuous operation device consisted of systems for the first stage reaction (liquefaction), solid-liquid separation, second stage reaction (hydrogenation), and solvent circulation. (NEDO)

  17. ANALYSIS OF THE KINETICS OF SOLVOLYSIS OF P-NITROPHENYLSULFONYLMETHYL PERCHLORATE IN BINARY ALCOHOLIC MIXTURES IN TERMS OF THE THERMODYNAMIC PROPERTIES OF THE SOLVENT MIXTURES

    Wijnen, J W; Engberts, J B F N; Blandamer, Michael J

    Rate constants are reported for the solvolysis of p-nitrophenylsulfonylmethyl perchlorate in binary ethanolic and methanolic mixtures at 298.2 K. Co-solvents include hydrocarbons, chlorinated hydrocarbons and 1,4-dioxane. The kinetic data are examined in terms of the effect of decreasing mole

  18. Calculation of carbon-14, chlorine-37, and deuterium kinetic isotope effects in the solvolysis of tert-butyl chloride

    Burton, G.W.; Sims, L.B.; Wilson, J.C.; Fry, A.

    1977-01-01

    In the solvolysis of tert-butyl chloride, satisfactory α-carbon-14, β-deuterium, and chlorine kinetic isotope effects (KIE) may be calculated for a productlike transition state characterized by bond orders n/sub C Cl/ = 0.2, n/sub C C/ = 1.18, and n/sub C H/ = 0.94, employing a diagonal valence force field, provided that allowance is made for hydrogen-bonded solvation of the developing chloride ion with n/sub Cl H/ approx. 0.05 (approx. 7 kcal/mole hydrogen bonds). The effect of the three solvating molecules appears to be to increase the ''effective'' mass of the incipient chloride ion and to decrease the loss of zero-point energy in going to the transition state. Reaction coordinates more complicated than a simple heterolysis of the carbon-chlorine bond appear to be unnecessary and there is no advantage in employing force fields more complex than a simple valence force field containing only diagonal elements for both the reactant and the transition state model. The structural and bonding features of the proposed transition state are in accord with earlier more qualitative conclusions concerning the polar nature and productlike character of the transition state, and provide a reasonable explanation of the kinetic and equilibrium isotope effects (EIE) for the reaction. An alternative transition state model involving weak solvent nucleophilic assistance provides reasonable calculated values for the KIE, but the EIE strongly suggest the importance of solvation of the leaving group which, together with the hyperconjugation of the β hydrogens, provides a preferred explanation of the tert-butyl solvolysis results

  19. Effect of process parameters on solvolysis liquefaction of Chlorella pyrenoidosa in ethanol–water system and energy evaluation

    Peng, Xiaowei; Ma, Xiaoqian; Lin, Yousheng; Wang, Xusheng; Zhang, Xiaoshen; Yang, Cheng

    2016-01-01

    Highlights: • Microalgae liquefaction in ethanol–water promoted bio-oil yield and property. • There existed synergistic effect between ethanol and water. • Ethanol contributed to deoxygenation and hydrogen-donating for bio-oil. • Net energy ratios of 20% and 40% ethanol were larger than pyrolysis technology. - Abstract: In this work, Chlorella pyrenoidosa was converted into bio-oil via solvolysis liquefaction in sub/supercritical ethanol–water system. The influence of reaction temperature (220–300 °C), retention time (0–120 min), solid/liquid ratio (6.3/75–50.0/75 g/mL) and ethanol content (0–100%) on bio-oil yield and property was investigated. The increase of reaction temperature and retention time both improved the bio-oil yield. The bio-oil yield increased firstly and then decreased when the solid/liquid ratio and ethanol content exceeded 18.8/75 g/mL and 80%, respectively. As the reaction temperature <260 °C and retention time <30 min, a soft and unsticky product was insoluble in dichloromethane (DCM) during the extraction process. The chemical composition of the DCM-insoluble product was analyzed by FTIR (Fourier Transform Infrared Spectrometry). The change tendency of O/C and H/C atomic ratio of bio-oil indicated that the addition of ethanol contributed to deoxygenation and hydrogen-donating for bio-oil, due to the dehydration and decarboxylation reaction. "1H NMR (hydrogen-1 nuclear magnetic resonance) analysis indicated that the main chemical compositions of bio-oil were aliphatic functional groups and heteroatomic functionalities (80.00–83.58%). The addition of ethanol enhanced the transesterification to form more ester. The NER (net energy ratio, the ratio of energy output to energy consumption) of solvolysis liquefaction in ethanol–water system (NER < 1) was less than that of hydrothermal liquefaction in sole water system (NER = 1.29), but the NERs of 20% and 40% ethanol content (NER = 0.91, 0.70 for 20% and 40% ethanol content

  20. FY 1999 Advanced research and development project under New Sunshine Project. Study on supercritical solvolysis reaction; 1999 nendo chorinkai ryutai riyo gijutsu sendo kenkyu kaihatsu seika hokokusho

    NONE

    2000-03-01

    The research and development project is implemented for the chemical processes which utilize supercritical fluids, in order to establish the basic technologies for the environment-friendly chemical processes. For the solvolysis, the conditions under which plastics are hydrolyzed in supercritical water are investigated, and the basic data are obtained for the optimum conditions under which thermoplastic resins are hydrolyzed. The mechanisms involved in hydrolysis of polymers in supercritical water are elucidated to some extent. The environment-friendly process for synthesizing polycarbonate in supercritical carbon dioxide gas is investigated, and the continuous flow sheets are established for securing almost 100% conversion in the presence of an inexpensive catalyst. For the oxidation, the tests are conducted to burn low-grade coal in supercritical water, and the conditions under which it is burnt without releasing acid and toxic gases are found. For the hydrogenation, heavy fuel oil is treated in supercritical water to produce the lighter products. The conditions under which light oils and gases are produced are clarified, and the basic data are obtained for producing light gases from the resultant coke as the by-product. (NEDO)

  1. Solvolysis of deuterium-labeled β-(syn-7-norbornenyl)ethyl p-bromobenzenesulfonates. Multiple cation automerizations in tight ion pairs

    Bly, R.S.; Bly, R.K.; Hamilton, J.B.; Jindal, S.P.

    1977-01-01

    The brosylates of α,α- 2 H 2 -, β,β- 2 H 2 -, and α,α,β,β- 2 H 4 -β-(syn-7-norbornenyl)ethanol have been prepared and solvolyzed at 25 0 C in buffered acetic acid, in buffered formic acid, and in buffered 90 percent acetone-water. The deuterated exo-2-brendyl and exo-4-brexyl derivatives produced in each case after a single hydrogen or deuterium shift have been converted to deuterated brendan-2-one and brexan-4-one mixtures and the position of the deuterium labels in each ketone determined mass spectrometrically. Comparison of the deuterium content of the brexan-4-one both before and after base-catalyzed exchange with protium permits analysis of the fractions of solvolysis product derived from each recognizably discrete rearranged cation. From these results it is clear that some hydrogen or deuterium migration occurs from each methylenic carbon of the starting brosylate and that 10 to 19 percent of those migrations are preceded by at least one Wagner--Meerwein automerization. It is suggested that the observed effect of the different solvents on the product distribution is due in part to ion pairing which affects the rate of transformations that change the net charge separation in the initial intermediate

  2. Correlation of the rates of solvolysis of α-bromoisobutyrophenone using both simple and extended forms of the Grunwald-Winstein equation and the application of correlation analysis to related studies.

    Kevill, Dennis Neil; Kim, Chang-Bae; D'Souza, Malcolm John

    2018-03-01

    A Grunwald-Winstein treatment of the specific rates of solvolysis of α-bromoisobutyrophenone in 100% methanol and in several aqueous ethanol, methanol, acetone, 2,2,2-trifluoroethanol (TFE), and 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP) mixtures gives a good logarithmic correlation against a linear combination of N T (solvent nucleophilicity) and Y Br (solvent ionizing power) values. The l and m sensitivity values are compared to those previously reported for α-bromoacetophenone and to those obtained from parallel treatments of literature specific rate values for the solvolyses of several tertiary mesylates containing a C(=O)R group attached at the α-carbon. Kinetic data obtained earlier by Pasto and Sevenair for the solvolyses of the same substrate in 75% aqueous ethanol (by weight) in the presence of silver perchlorate and perchloric acid are analyzed using multiple regression analysis.

  3. Tyre Recycling with Thermal Solvolysis Method Using Microwave Radiation

    Korjakins, Aleksandrs; Holimenkovs, Aleksandrs

    2017-01-01

    Used tyres are one of the most widespread types of waste and one of the polymer materials which are most difficult to recycle. There are many different applications for used tyres today. Part of the tyres can be retreated and re-used, but most of the used tyres are recycled. By dissolving the tyres, it is possible to filter out various chemical substances. These substances coming from the used tyres can be used for creating a new material or improving an existing one. One of the technologies ...

  4. Enhanced Oxidation and Solvolysis Reactions in Chemically Inert Microheterogeneous Systems.

    1987-01-13

    Mackay, Adv.Coll.Interf.Sc{. 15, 131 (1981) 11 C. Bodea and J. Silberg , "Recent Advances in the Chemistry of Phenothiazines" in "Advances in Heterocyclic... Chemistry ", A.R. Katritzky and A.J. Boulton, , eds., Vol. 9, Academic Press, New York, 1968, p. 321 12 A.M. Braun, M.-A. Gilson, M. Krieg, M.-T

  5. Direct liquefaction of wood through solvolysis and catalytic hydrodeoxygenation: an engineering assessment

    Moffat, J.M.; Overend, J.P.

    1985-01-01

    Liquefaction of wood to produce fuel and chemical intermediates has been intensively studied over the last decade. The results of Canadian research into process feasibility are presented on the basis of two studies, the first in 1980 utilizing data of the mid-70s and the other on the basis of research conducted up to 1982. The earlier study was for a single reactor concept in which catalyst, wood and hydrogen were reacted to produce a proto-oil, while the later study embodies a two-stage concept involving dissolution of the polymer matrix followed by fractionation and catalytic upgrading using hydrodeoxygenation. Increased knowledge of the characteristics of the first stage products show that there are many component mixtures containing between 10 and 20% oxygen. Most of the oxygen is in aromatic phenol-type structures with some ether linkages, and low severity processes to deoxygenate the product while increasing the hydrogen to carbon ratio are called for. The economic prospects for a two-stage process are described on the basis of a hydrocarbon process proposed by HRI International for Kraft process lignin. These show that a mix of BTX products and fuel oil could generate a profitable rate of return. 62 references.

  6. Theoretical Study of the Microhydration of Mononuclear and Dinuclear Uranium(VI) Species Derived from Solvolysis of Uranyl Nitrate in Water

    Ončák, Milan; Schröder, Detlef; Slavíček, Petr

    2010-01-01

    Roč. 31, č. 12 (2010), s. 2294-2306 ISSN 0192-8651 R&D Projects: GA ČR GA203/08/1487; GA ČR GA203/09/0422 Institutional research plan: CEZ:AV0Z40400503; CEZ:AV0Z40550506 Keywords : density functional thoery * ion association * metal hydration Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 4.050, year: 2010

  7. MICROWAVE INDUCED DEGRADATION OF GLASS FIBER REINFORCED POLYESTER FOR FIBER AND RESIN RECOVERY

    Ucar, Hülya; Nielsen, Rudi Pankratz; Søgaard, Erik Gydesen

    A solvolysis process to depolymerize the resin in glass fiber reinforced composites and recover the glass fibers has been investigated using microwave induced irradiation. The depolymerization was carried out in HNO3 with concentrations in the range of 1M-7M and in KOH with concentrations ranging...

  8. JCSC_129_08_1301_1317_SI.docx

    chandan

    Solvolysis of organophosphorus pesticide parathion with simple and α nucleophiles: A theoretical study. CHANDAN SAHU and ABHIJIT K DAS*. Department of Spectroscopy, Indian Association for the Cultivation of Science, Jadavpur, Kolkata, West Bengal 700 032, India. Email: spakd@iacs.res.in. *For Correspondence.

  9. Study of the Kinetics of an S[subscript N]1 Reaction by Conductivity Measurement

    Marzluff, Elaine M.; Crawford, Mary A.; Reynolds, Helen

    2011-01-01

    Substitution reactions, a central part of organic chemistry, provide a model system in physical chemistry to study reaction rates and mechanisms. Here, the use of inexpensive and readily available commercial conductivity probes coupled with computer data acquisition for the study of the temperature and solvent dependence of the solvolysis of…

  10. Rate and Product Studies of Solvolyses of Benzyl Fluoroformate

    Dennis N. Kevill

    2006-07-01

    Full Text Available The specific rates of solvolysis of benzyl fluoroformate have been measured inseveral hydroxylic solvents at 25.0 °C. For methanolysis, the solvent deuterium isotopeeffect and activation parameters were determined and activation parameters were alsodetermined for solvolyses in ethanol and 80% ethanol. For several of the binary hydroxylicsolvents, measurement of product ratios allowed selectivity values to be determined. Anextended Grunwald–Winstein treatment of the data led to sensitivities to changes in solventnucleophilicity and ionizing power. Comparison with previously determined specific ratesfor solvolysis of the chloroformate gave fluorine/chlorine rate ratios greater than unity. Allof the determinations made were consistent with an addition–elimination (association–dissociation mechanism, with addition rate-determining.

  11. Optimised deconjugation of androgenic steroid conjugates in bovine urine

    Pedersen, Mikael; Frandsen, Henrik Lauritz; Andersen, Jens Hinge

    2017-01-01

    and glucuronidase resulting in free steroids in the extract. It is well known that some sulphates are not deconjugated using aryl sulphatase; instead, for example, solvolysis can be used for deconjugation of these aliphatic sulphates. The effectiveness of solvolysis on androgenic steroid sulphates was tested......After administration of steroids to animals the steroids are partially metabolised in the liver and kidney to phase 2 metabolites, i.e., glucuronic acid or sulphate conjugates. During analysis these conjugated metabolites are normally deconjugated enzymatically with aryl sulphatase...... with selected aliphatic steroid sulphates (boldenone sulphate, nortestosteron sulphate and testosterone sulphate), and the method was validated for analysis of androgenic steroids in bovine urine using free steroids, steroid sulphates and steroid glucuronides as standards. Glucuronidase and sulphuric acid...

  12. Noncatalytic Direct Liquefaction of Biorefinery Lignin by Ethanol

    Nielsen, Joachim Bachmann; Jensen, Anders; Madsen, Line Riis

    2017-01-01

    There is a growing interest in lignin valorization to biofuels and chemicals. Here, we propose a novel and simple noncatalytic process to directly liquefy lignin rich solid residual from second generation bioethanol production by solvolysis with ethanol. Through an extensive parameter study...... in batch autoclaves assessing the effects of varying reaction temperature, reaction time, and solvent:lignin ratio, it is shown that hydrothermally pretreated enzymatic hydrolysis lignin solvolysis in supercritical ethanol can produce a heptane soluble bio-oil without the need for exhaustive deoxygenation....... The process does not require addition of catalyst or a reducing agent such as hydrogen. The process is advantageously carried out with a low reaction period ((ethanol:lignin (w/w) ratio of 2:1) which is a previously unexplored domain for lignin...

  13. A nuclear magnetic resonance and electron spin resonance study on the dynamics of pentacoordinated organophosphorus compounds

    Keijzer, A.E.H. de.

    1988-01-01

    In this thesis the role of the steric and electronic effects on the fundamental dynamic behaviour of pentacoordinated phosporus compounds is further elaborated. In chapter 2 a variable temperature 13 C NMR study, performed on a series of monocyclic oxyphosphoranes, is presented. The investigations were carried out to determine the influence of the conformational transmission effect on the barriers to pseudorotation in pentacoordinated phosphorus compounds. Chapter 3 also comprises a variable temperature 13 C NMR study on pentacoordinated phosphorus compounds. In this chapter, however, an additional high-resolution 1 H NMR study on the conformational equilibria around the P-O-C-C-O fragments is included. These studies were performed in order to determine whether the enhancement of the reorganization rates around phosphorus is brought about by accelerated pseudorotation or by the involvement of hexacoordinated zwitterionic phosphorus intermediates. In chapter 4, a 31 P NMR study on the solvolysis rate of several phosphinate esters is described. This study was performed in order to determine the influence of the conformational transmission effect on the solvolysis rate of phosphate esters. A number of phosphates is examined in which, during the course of the solvolysis reaction, the conformational transmission effect is bound to be present or absent respectively. Moreover, it is discussed in which way the concept of conformational transmission induced differences in solvolysis rates can be used as a probe to examine the reactions of biologically important phosphate esters. In chapters 5 and 6 ESR studies on the influence of steric and electronic factors on phosphoranyl formation in solution, and on the intramolecular electron transfer in phosphoranyl radicals are presented. (author). 121 refs.; 33 figs.; 17 figs

  14. Simple method for fast deprotection of nucleosides by triethylamine-catalyzed methanolysis of acetates in aqueous medium

    Meier, Lidiane; Monteiro, Gustavo C.; Baldissera, Rodrigo A.M.; Sa, Marcus Mandolesi

    2010-01-01

    A straightforward methodology for deacetylation of protected ribonucleosides was developed based on triethylamine-catalyzed solvolysis in aqueous methanol. Reactions are completed in a few minutes under microwave irradiation and the free nucleosides are obtained in high yield after simple evaporation of volatiles. Other important features include the involvement of readily available reagents and the compatibility with diverse functional groups, which make this process very attractive for broad application. (author)

  15. Development of Composite Case Salvage Procedures

    1982-04-01

    impacted by the high pressure water. Figure 25 shows damage to EPDM rubber from an MX case. Figure 26 shows the effect of the water on the V-45 ( NBR ... Rubber plus Polyester plus Degradation Elastomer Polyether Cleavage Recycling Reclamation Solvolysis Also: Salvage Rubber Reclamation Elastomers... rubber . 2. Analysis of the material extracted from the insu- lation showed that plasticizer (phthalates) was removed by the solvents. 3. After

  16. The selective recycling of mixed plastic waste of polylactic acid and polyethylene terephthalate by control of process conditions

    Carné Sánchez, Arnau; Collinson, Simon R.

    2011-01-01

    The glycolysis of postconsumer polyethylene terephthalate (PET) waste was evaluated with catalysts of zinc acetate, zinc stearate and zinc sulfate, showing that zinc acetate was the most soluble and effective. The chemical recycling by solvolysis of polylactic acid (PLA) and PET waste in either methanol or ethanol was investigated. Zinc acetate as a catalyst was found to be necessary to yield an effective depolymerization of waste PLA giving lactate esters, while with the same reaction condit...

  17. Fast cleavage of phycocyanobilin from phycocyanin for use in food colouring

    Roda-Serrat, Maria Cinta; Christensen, Knud Villy; El-Houri, Rime

    2018-01-01

    Phycocyanins from cyanobacteria are possible sources for new natural blue colourants. Their chromophore, phycocyanobilin (PCB), was cleaved from the apoprotein by solvolysis in alcohols and alcoholic aqueous solutions. In all cases two PCB isomers were obtained, while different solvent adducts were......, and microwave assisted reaction. The sealed vessel method is a new approach for fast cleavage of PCB from phycocyanin and gave at 120°C the same yield within 30 min compared to 16 hours by the conventional reflux method (P

  18. Nucleofugalities of Neutral Leaving Groups in 80 % Aqueous Acetonitrile

    Sandra Jurić

    2016-06-01

    Full Text Available Nucleofugalites of tetrahydrothiophene, dimethyl sulfide and differently substituted pyridines in 80 % aqueous acetonitrile have been derived from the SN1 solvolysis rate constants of the corresponding X,Y-substituted benzhydryl derivatives (1–10. In sol-volysis of sulfonium ions in 80 % aqueous acetonitrile, where acetonitrile is a good cation solvator, the solvation of the reactant ground state is an important rate determining variable since the positive charge is almost entirely located on the leaving group. As a consequence, reaction rates of sulfonium ions are more sensitive to the substrate structure in 80 % aqueous acetonitrile than in pure and aqueous alcohols, which are less efficient as cation solvators. In solvolysis of pyridinium ions the solvation of the reactant ground state is less important, since the positive charge is considerably distributed between the carbon at the reaction center and the leaving group. In such cases the important rate determining variable is solvation of the transition state. Slower reactions of pyridinium sub-strates progress over later, carbocation-like transition states in which the solvation is more important, so those substrates solvolyze slightly faster in aqueous acetonitrile than in methanol (k80AN > kM. Faster reactions proceed over earlier TS in which the solvation is diminished, so those substrates solvolyze somewhat faster in methanol than in aqueous acetonitrile (k80AN kM. This work is licensed under a Creative Commons Attribution 4.0 International License.

  19. Summary of FY 1980 results of Sunshine Project. Development of coal liquefaction techniques; 1980 nendo sekitan ekika gijutsu no kaihatsu seika hokokusho. Sunshine keikaku itaku kenkyu kaihatsu

    NONE

    1981-03-01

    This report summarizes the results of the 3 R and D themes for coal liquefaction techniques, pursued by the Sunshine Project; (1) development of solvent extraction type liquefaction plant, and brown coal liquefaction technique R and D demonstration surveys, (2) development of solvolysis type liquefaction plant, and (3) development of direct hydrogenation type liquefaction plant. For the theme (1), the 1 T/D test plant, solid/liquid separator and small-size continuous settlement separator are constructed, and partly completed. The elementary studies include solvent extraction type liquefaction process, materials for coal liquefaction plant and solid/liquid separation. Australia's Victoria brown coal and Chinese coal are studied to clarify the possible problems involved in liquefaction of these coal species for commercialization of the liquefaction techniques in the early stage. The elementary techniques studied include dehydration of brown coal, milling at high temperature in oil, de-ashing, and secondary and primary hydrogenation. For the theme (2), the 1 T/D plant is inspected and maintained to clarify the problems involved in the continuous operation, revamped and repaired as necessary, given preventive maintenance, and tested for operability confirmation. The elementary studies include solvolysis type liquefaction process, scale-up, hydrogenation plant for solvolysis pitch. For the item (3), the 2.4 T/D test plant is constructed, and the elementary studies are conducted, for, e.g., liquefaction reactions in the presence of an iron-based catalyst. (NEDO)

  20. Summary of FY 1980 results of Sunshine Project. Development of coal liquefaction techniques; 1980 nendo sekitan ekika gijutsu no kaihatsu seika hokokusho. Sunshine keikaku itaku kenkyu kaihatsu

    NONE

    1981-03-01

    This report summarizes the results of the 3 R and D themes for coal liquefaction techniques, pursued by the Sunshine Project; (1) development of solvent extraction type liquefaction plant, and brown coal liquefaction technique R and D demonstration surveys, (2) development of solvolysis type liquefaction plant, and (3) development of direct hydrogenation type liquefaction plant. For the theme (1), the 1 T/D test plant, solid/liquid separator and small-size continuous settlement separator are constructed, and partly completed. The elementary studies include solvent extraction type liquefaction process, materials for coal liquefaction plant and solid/liquid separation. Australia's Victoria brown coal and Chinese coal are studied to clarify the possible problems involved in liquefaction of these coal species for commercialization of the liquefaction techniques in the early stage. The elementary techniques studied include dehydration of brown coal, milling at high temperature in oil, de-ashing, and secondary and primary hydrogenation. For the theme (2), the 1 T/D plant is inspected and maintained to clarify the problems involved in the continuous operation, revamped and repaired as necessary, given preventive maintenance, and tested for operability confirmation. The elementary studies include solvolysis type liquefaction process, scale-up, hydrogenation plant for solvolysis pitch. For the item (3), the 2.4 T/D test plant is constructed, and the elementary studies are conducted, for, e.g., liquefaction reactions in the presence of an iron-based catalyst. (NEDO)

  1. [Bis(TrimethylsilylMethyl]Lithium and -Sodium: Solubility in Alkanes and Complexes with O- and N- Donor Ligands

    Markus von Pilgrim

    2017-06-01

    Full Text Available In contrast to alkyl compounds of lithium, which play an important role in organometallic chemistry, the corresponding heavier alkali metal compounds are less investigated. These compounds are mostly insoluble in inert solvents or undergo solvolysis in coordinating solvents due to their high reactivity. An exception from this typical behavior is demonstrated by bis(trimethylsilylmethylsodium. This study examines alkane solutions of bis(trimethylsilylmethyllithium and -sodium by NMR spectroscopic and cryoscopic methods. In addition, structural studies by X-ray crystallography of the corresponding compounds coordinated by O- and N- ligands (tetrahydrofuran and tetramethylethylenediamine present possible structural motifs of the uncoordinated compounds in solution.

  2. FY 1998 'The New Sunshine Project' leading R and D. Report on the results of the leading R and D of supercritical fluid utilization technology; 1998 nendo 'New Sunshine Keikaku' sendo kenkyu kaihatsu. Chorinkai ryutai riyo gijutsu sendo kenkyu kaihatsu seika hokokusho

    NONE

    1999-03-01

    The paper reported the FY 1998 achievement of the supercritical fluid utilization leading R and D which started in FY 1997 on a 3-year plan. In the R and D, solvolysis reaction, oxidation reaction and hydrogenation reaction were taken up in the chemical process using supercritical fluid. In the study of solvolysis reaction, the basic data were obtained on decomposition conditions of thermoplastic and thermosetting plastics in supercritical water. Further, concerning the synthesis of environmental friendly type carbonate using CO2, a conversion rate of almost 100% was obtained. About the oxidation reaction, conditions were found out for burning low grade coal in supercritical water without emitting acid gas. This is considered to lead to a possibility of the supercritical water power generation. Relating to the hydrogenation reaction, a study was made on lightening technology of heavy distillate using supercritical water, and the conditions for effective emission of methane and hydrogen were found out. As to the base technology, a study was made of metal materials with high corrosion resistance against supercritical water. (NEDO)

  3. FY 1998 'The New Sunshine Project' leading R and D. Report on the results of the leading R and D of supercritical fluid utilization technology; 1998 nendo 'New Sunshine Keikaku' sendo kenkyu kaihatsu. Chorinkai ryutai riyo gijutsu sendo kenkyu kaihatsu seika hokokusho

    NONE

    1999-03-01

    The paper reported the FY 1998 achievement of the supercritical fluid utilization leading R and D which started in FY 1997 on a 3-year plan. In the R and D, solvolysis reaction, oxidation reaction and hydrogenation reaction were taken up in the chemical process using supercritical fluid. In the study of solvolysis reaction, the basic data were obtained on decomposition conditions of thermoplastic and thermosetting plastics in supercritical water. Further, concerning the synthesis of environmental friendly type carbonate using CO2, a conversion rate of almost 100% was obtained. About the oxidation reaction, conditions were found out for burning low grade coal in supercritical water without emitting acid gas. This is considered to lead to a possibility of the supercritical water power generation. Relating to the hydrogenation reaction, a study was made on lightening technology of heavy distillate using supercritical water, and the conditions for effective emission of methane and hydrogen were found out. As to the base technology, a study was made of metal materials with high corrosion resistance against supercritical water. (NEDO)

  4. Structure and gene cluster of the O-antigen of Escherichia coli O54.

    Naumenko, Olesya I; Guo, Xi; Senchenkova, Sof'ya N; Geng, Peng; Perepelov, Andrei V; Shashkov, Alexander S; Liu, Bin; Knirel, Yuriy A

    2018-06-15

    Mild acid hydrolysis of the lipopolysaccharide of Escherichia coli O54 afforded an O-polysaccharide, which was studied by sugar analysis, solvolysis with anhydrous trifluoroacetic acid, and 1 H and 13 C NMR spectroscopy. Solvolysis cleaved predominantly the linkage of β-d-Ribf and, to a lesser extent, that of β-d-GlcpNAc, whereas the other linkages, including the linkage of α-l-Rhap, were stable under selected conditions (40 °C, 5 h). The following structure of the O-polysaccharide was established: →4)-α-d-GalpA-(1 → 2)-α-l-Rhap-(1 → 2)-β-d-Ribf-(1 → 4)-β-d-Galp-(1 → 3)-β-d-GlcpNAc-(1→ The O-antigen gene cluster of E. coli O54 was analyzed and found to be consistent in general with the O-polysaccharide structure established but there were two exceptions: i) in the cluster, there were genes for phosphoserine phosphatase and serine transferase, which have no apparent role in the O-polysaccharide synthesis, and ii) no ribofuranosyltransferase gene was present in the cluster. Both uncommon features are shared by some other enteric bacteria. Copyright © 2018 Elsevier Ltd. All rights reserved.

  5. FY 1981 Report on the results of Sunshine Project. Coal energy; 1981 nendo sunshine keikaku seika hokokusho. Sekitan energy

    NONE

    1981-07-01

    This report presents the results of (researches on solvolysis liquefaction mechanisms and reaction promotion with oil- and coal-based solvents), conducted as part of the research and development project for coal liquefaction techniques. The FY 1981 program includes researches on (1) the effects of liquefaction reaction conditions on liquefaction yield and production of light products for coal species of low degree of carbonization, including brown coal, (2) the effects of pretreatment of coal on its liquefaction reactivity, and (3) up-grading of the solvolysis coal liquid (SCL). For the item (1), HA240 (hydrogenated Ashland's A240) is used to investigate its liquefaction capacity for various coal species of low degree of carbonization, including brown coal. For the item (2), the effects of pretreatment in a hot water bath with reflux was investigated for sub-bituminous coal in the FY 1980. In the FY 1981, various pretreatment methods are attempted for enhancing liquefaction reactivity of brown coal. As a result, it is found that ash content of brown coal is decreased to one-third of the initial level, when it is treated in a diluted hydrochloric acid bath with reflux. For the item (3), SCL hydrogenated by Birch reduction (B-SCL, 1) is compared with H-SCL with respect to properties, structures and thermal crackability, to discuss the items required for the catalyst to be used in the second stage by clarifying effectiveness of the catalyst. (NEDO)

  6. Unimolecular Solvolyses in Ionic Liquid: Alcohol Dual Solvent Systems

    Elizabeth D. Kochly

    2016-01-01

    Full Text Available A study was undertaken of the solvolysis of pivaloyl triflate in a variety of ionic liquid:alcohol solvent mixtures. The solvolysis is a kΔ process (i.e., a process in which ionization occurs with rearrangement, and the resulting rearranged carbocation intermediate reacts with the alcohol cosolvent via two competing pathways: nucleophilic attack or elimination of a proton. Five different ionic liquids and three different alcohol cosolvents were investigated to give a total of fifteen dual solvent systems. 1H-NMR analysis was used to determine relative amounts of elimination and substitution products. It was found, not surprisingly, that increasing the bulkiness of alcohol cosolvent led to increased elimination product. The change in the amount of elimination product with increasing ionic liquid concentration, however, varied greatly between ionic liquids. These differences correlate strongly, though not completely, to the Kamlet–Taft solvatochromic parameters of the hydrogen bond donating and accepting ability of the solvent systems. An additional factor playing into these differences is the bulkiness of the ionic liquid anion.

  7. Preparation of compounds AWCl6 from WCl6 in Cl--containing solvents

    Seifert, H.J.; Kiewisch, B.; Wuesteneck, A.

    1977-01-01

    In Glyme, ACN or CH 2 Cl 2 WCl 6 is reduced by Cl - to WCl 6 - . From those solutions compounds AWCl 6 can be isolated with A = Cs (Glyme, ACN), A = Rb, K, NH 4 (ACN) and A = N(C 2 H 5 ) 4 (CH 2 Cl 2 ). By concentrating of glyme-solutions a precipitate of A 2 WCl 6 is formed by disproportionation. In methanol/HCl also solvolysis to oxo-compounds of W 6+ takes place as function of the H + -concentration. With N(C 2 H 5 ) 4 Cl not only chlorotungstates but also methoxy- and oxo-spezies of W 5+ can be isolated. (author)

  8. Poly(ethylene terephthalate)-based carbons as electrode material in supercapacitors

    Domingo-Garcia, M.; Almazan-Almazan, M.C.; Lopez-Garzon, F.J. [Dpto de Quimica Inorganica, Facultad de Ciencias, 18071 Granada (Spain); Fernandez, J.A.; Centeno, T.A. [Instituto Nacional del Carbon-CSIC, Apartado 73, 33080 Oviedo (Spain); Stoeckli, F. [Physics Department, University of Neuchatel, Rue Emile Argand 11, CH-2009 Neuchatel (Switzerland)

    2010-06-15

    A systematic study by complementary techniques shows that PET-waste from plastic vessels is a competitive precursor of carbon electrodes for supercapacitors. PET derived-activated carbons follow the general trends observed for highly porous carbons and display specific capacitances at low current density as high as 197 F g{sup -1} in 2 M H{sub 2}SO{sub 4} aqueous electrolyte and 98 F g{sup -1} in the aprotic medium 1 M (C{sub 2}H{sub 5}){sub 4}NBF{sub 4}/acetonitrile. Additionally, high performance has also been achieved at high current densities, which confirms the potential of this type of materials for electrical energy storage. A new method based on the basic solvolysis of PET-waste and the subsequent carbonization seems to be an interesting alternative to obtain porous carbons with enhanced properties for supercapacitors. (author)

  9. Release of volatile mercury from vascular plants

    Siegel, S. M.; Puerner, N. J.; Speitel, T. W.

    1974-01-01

    Volatile, organic solvent soluble mercury has been found in leaves and seeds of several angiosperms. Leaves of garlic vine, avocado, and haole-koa release mercury in volatile form rapidly at room temperature. In garlic vine, the most active release is temperature dependent, but does not parallel the vapor-pressure temperature relationship for mercury. Mercury can be trapped in nitric-perchloric acid digestion fluid, or n-hexane, but is lost from the hexane unless the acid mixture is present. Seeds of haole-koa also contain extractable mercury but volatility declines in the series n-hexane (90%), methanol (50%), water (10%). This suggests that reduced volatility may accompany solvolysis in the more polar media.

  10. Flowthrough Reductive Catalytic Fractionation of Biomass

    Anderson, Eric M.; Stone, Michael L.; Katahira, Rui; Reed, Michelle; Beckham, Gregg T.; Román-Leshkov, Yuriy

    2017-11-01

    Reductive catalytic fractionation (RCF) has emerged as a leading biomass fractionation and lignin valorization strategy. Here, flowthrough reactors were used to investigate RCF of poplar. Most RCF studies to date have been conducted in batch, but a flow-based process enables the acquisition of intrinsic kinetic and mechanistic data essential to accelerate the design, optimization, and scale-up of RCF processes. Time-resolved product distributions and yields obtained from experiments with different catalyst loadings were used to identify and deconvolute events during solvolysis and hydrogenolysis. Multi-bed RCF experiments provided unique insights into catalyst deactivation, showing that leaching, sintering, and surface poisoning are causes for decreased catalyst performance. The onset of catalyst deactivation resulted in higher concentrations of unsaturated lignin intermediates and increased occurrence of repolymerization reactions, producing high-molecular-weight species. Overall, this study demonstrates the concept of flowthrough RCF, which will be vital for realistic scale-up of this promising approach.

  11. Depolymerization of post-consumer PET with multifunctional alcohol through melt processing; Despolimerizacao de PET pos-consumo com alcool multifuncional atraves de processamento por fusao

    Lessa, Tathiane C.R.F.; Mendes, Luis C.; Dias, Marcos L., E-mail: tathianecr@ima.ufrj.b [Universidade Federal do Rio de Janeiro (IMA/UFRJ), RJ (Brazil). Inst. de Macromoleculas Professora Eloisa Mano. Centro de Tecnologia

    2009-07-01

    The purpose of this study was to prepare oligomers from post-consumer PET with multifunctional alcohol, through melt processing, aiming to develop a new material, able to play a role as filler or property modifier. Maintaining constants the process conditions, content and kind of catalyst, the influence of the solvolysis agent on the PET depolymerization was investigated. The products were evaluated by wide-angle X-ray diffraction (WAXD) and thermogravimetry (TG/DTG). The changes in the WAXD curves and the shift of the maximum degradation temperature suggested that the ester linkages were broken being the ethylene glycol moieties replaced with hydroxyl-terminal groups of the multifunctional alcohol, as result of a transesterification reaction. The chemical structure of the new ester was named 'star-branching polymer'. (author)

  12. Depolymerization of post-consumer PET with multifunctional alcohol through melt processing

    Lessa, Tathiane C.R.F.; Mendes, Luis C.; Dias, Marcos L.

    2009-01-01

    The purpose of this study was to prepare oligomers from post-consumer PET with multifunctional alcohol, through melt processing, aiming to develop a new material, able to play a role as filler or property modifier. Maintaining constants the process conditions, content and kind of catalyst, the influence of the solvolysis agent on the PET depolymerization was investigated. The products were evaluated by wide-angle X-ray diffraction (WAXD) and thermogravimetry (TG/DTG). The changes in the WAXD curves and the shift of the maximum degradation temperature suggested that the ester linkages were broken being the ethylene glycol moieties replaced with hydroxyl-terminal groups of the multifunctional alcohol, as result of a transesterification reaction. The chemical structure of the new ester was named 'star-branching polymer'. (author)

  13. Catalytic Upgrading of Thermochemical Intermediates to Hydrocarbons: Conversion of Lignocellulosic Feedstocks to Aromatic Fuels and High Value Chemicals

    Cortright, Randy [Virent, Inc., Madison, WI (United States); Rozmiarek, Bob [Virent, Inc., Madison, WI (United States); Van Straten, Matt [Virent, Inc., Madison, WI (United States)

    2017-11-28

    The principal objective of this project was to develop a fully integrated catalytic process that efficiently converts lignocellulosic feedstocks (e.g. bagasse, corn stover, and loblolly pine) into aromatic-rich fuels and chemicals. Virent led this effort with key feedstock support from Iowa State University. Within this project, Virent leveraged knowledge of catalytic processing of sugars and biomass to investigate two liquefaction technologies (Reductive Catalytic Liquefaction (USA Patent No. 9,212,320, 2015) and Solvolysis (USA Patent No. 9,157,030, 2015) (USA Patent No. 9,157,031, 2015)) that take advantage of proprietary catalysts at temperatures less than 300°C in the presence of unique solvent molecules generated in-situ within the liquefaction processes.

  14. Detailed kinetic and heat transport model for the hydrolysis of lignocellulose by anhydrous hydrogen fluoride vapor

    Rorrer, G.L.; Mohring, W.R.; Lamport, D.T.A.; Hawley, M.C.

    1988-01-01

    Anhydrous Hydrogen Fluoride (HF) vapor at ambient conditions efficiently and rapidly hydrolyzed lignocellulose to glucose and lignin. The unsteady-state reaction of HF vapor with a single lignocellulose chip was mathematically modeled under conditions where external and internal mass-transfer resistances were minimized. The model incorporated physical adsorption of HF vapor onto the lignocellulosic matrix and solvolysis of cellulose to glucosyl fluoride by adsorbed HF into the differential material and energy balance expressions. Model predictions for the temperature distribution and global glucose yield in the HF-reacting lignocellulose chip as a function of reaction time and HF vapor stream temperature agreed reasonably with the complimentary experimental data. The model correctly predicted that even when mass-transfer resistances for the reaction of HF vapor with a single lignocellulose chip are minimized, external and internal heat-transfer resistances are still significant.

  15. Secondary partitioning isotope effects on solvolytic ion pair intermediates

    Abbey, K.J.

    1976-01-01

    The thermal decomposition of N-benzhydryl N-nitrosobenzamide (BNB) has been shown to produce an ion pair which either forms ester or reacts with the solvent. In ethanol, the fraction of ester produced, R, was much smaller than R values obtained from solvolysis or from the diphenyldiazomethane (DDM)-benzoic acid reaction, which was suggested to yield the same ion pair as solvolysis. This difference led to the conclusion that the ionic species for the nitrosamide decomposition is a nitrogen-separated ion pair. This study was initiated on the assumption that BNB led to solvolytic ion pairs, but that both the intimate and solvent-separated ion pairs were produced directly from the nitrosamide. The use of α-tritiated BNB for the study of partitioning isotope effects (PIE's) in this system led to activity ratios much lower than expected from other reported work. Results of studies of ''special'' salt effect were not consistent for all situations, but the results do suggest that the assumption that BNB leads to solvolytic ion pairs is probably valid. The investigation of the more stable p-methoxybenzhydryl benzoate system proved to be highly productive. The ester fraction produced, R, responded dramatically to the addition of common-ion as well as ''special'' salts. The functional relationship of R on salt concentration could be explained in terms of Winstein's solvolytic scheme where the intimate ion pair, the solvent-separated ion pair, and the dissociated ion were important. Tritium-labelled compounds were used for PIE studies on 3 different compounds, and three different methods of reaction are proposed

  16. Report on results of R and D of coal liquefaction technology in fiscal 1981; 1981 nendo sekitan ekika gijutsu no kenkyu kaihatsu seika setsumeisho

    NONE

    1982-03-01

    This paper explains the results of development of coal liquefaction technology under the Sunshine Project in fiscal 1981. In connection with solvent extraction and liquefaction, an 1 t/day experimental plant was completed for bituminous coals and operated continuously for 153 hours. An examination also started for the development of a 250 t/day pilot plant. As the element studies, R and D is in progress on the solvent extraction and liquefaction process, solid-liquid separation, secondary hydrogenation, and plant materials. In brown coals, the construction work of a 50 t/day pilot plant started for the purpose of establishing liquefaction technology for brown coal in Victoria State, Australia, with a part of the equipment manufactured. As the element studies, research was conducted on primary hydrogenation, deliming, secondary hydrogenation, dehydration and catalysts. In solvolysis liquefaction, a short-time concluding liquefaction reaction was continuously performed by a plant of 1 t/day scale. In direct hydro-liquefaction, a 2.4 t/day experimental plant was constructed, with the element studies conducted successively. In other words, researches were carried out by the bench scale plant on liquefaction, solid-liquid separation, iron-based catalysts, catalyst and reutilization, motive force recovery system by hydrohoist, and effect of preheating and deaeration. (NEDO)

  17. Potentiometric titrations in anhydrous acetic acid

    Le Port, L.

    1966-03-01

    The method used for studying anhydrous acetic acid is potentiometry with a glass electrode. We have in this way studied the titration of common inorganic acids (HClO 4 - HBr - H 2 SO 4 - HCl - HNO 3 - H 3 PO 4 ) and of some metallic salts. Furthermore we have shown that complex acids are formed between HCl and some metallic chlorides. An analysis of the titration curves for the inorganic acids against pyridinium chloride has made it possible to calculate a certain number of values for the dissociation pK of these acids and of the corresponding pyridinium salts. The titration of metallic perchlorates constitutes a method of studying the stability of acetates; we have thus been able to draw up a classification for some of these acetates. The metallic chlorides studied fall into two groups according to their behaviour in weak or strong acids. The differences have been explained on the basis of the role played by solvolysis. In the third part we have studied the acidic properties of mixtures of HCl with certain metallic chlorides. This work has demonstrated the existence, in certain cases, of acid complexes of the type (HCl) m MCl n . (author) [fr

  18. Aromatic chemical feedstocks from coal

    Collin, G

    1982-06-01

    Liquid byproducts of coal carbonization meet some 25% of the world demand for aromatic chemicals, currently at approx. 30 million t/a, in particular 15% of the demand for benzene and over 95% of the demand for condensed aromatics and heteroaromatics. Industrial processing of the aromatic byproducts of coal pressure gasification is carried out to only a minor extent. Other methods that may be employed in future to obtain carbochemical aromatic compounds are solvolysis and supercritical gas extraction, the catalytic liquid-phase hydrogenation and hydropyrolysis of coal, which also permit recovery of benzene and homologues, phenols, and condensed and partially hydrogenated aromatics, and the synthesis of aromatics using methanol as the key compound. As with the present means of obtaining aromatic chemicals from coal, the processes that may in the future be applied on an industrial scale to obtain pure aromatics will only be economically feasible if linked with the manufacture of other mass products and combined with the present production of carbochemical aromatics.

  19. Aromatic raw materials from coal

    Collin, G

    1982-06-01

    Liquid byproducts of coal carbonization meet some 25% of the world demand for aromatic chemicals, currently at approx. 30 million t/a, in particular 15% of the demand for benzene and over 95% of the demand for condensed aromatics and heteroaromatics. Industrial processing of the aromatic byproducts of coal pressure gasification is carried out to only a minor extent. Other methods that may be employed in future to obtain carbochemical aromatic compounds are solvolysis and supercritical gas extraction, the catalytic liquid-phase hydrogenation and hydropyrolysis of coal, which also permit recovery of benzene and homologues, phenols, and condensed and partially hydrogenated aromatics, and the synthesis of aromatics using methanol as the key compound. As with the present means of obtaining aromatic chemicals from coal, the processes that may in future be applied on an industrial scale to obtain pure aromatics will only be economically feasible if linked with the manufacture of other mass products and combined with the present production of carbochemical aromatics. (In German)

  20. Effect of Reaction Conditions on the Surface Modification of Cellulose Nanofibrils with Aminopropyl Triethoxysilane

    Eduardo Robles

    2018-04-01

    Full Text Available Nine different surface modifications of cellulose nanofibrils (CNF with 3-aminopropyl triethoxysilane (ATS by using three different solvent systems (water, ethanol, and a mixture of both were investigated. The effect of reaction conditions, such as silane to cellulose ratio and solvent type were evaluated to determine their contribution to the extent of the silane modification. Nanofibril properties were evaluated by infrared spectroscopy, powder X-ray diffraction, surface free energy, thermogravimetry, 13C and 29Si nuclear magnetic resonance, and electronic microscopy. The influence of the solvent in the solvolysis of the silane was reflected in the presence or absence of ethoxy groups in the silane. On the other hand, whereas the surface modification was increased directly proportionally to silane ratio on the reaction, the aggregation of nanofibrils was also increased, which can play a negative role in certain applications. The increment of silane modification also had substantial repercussions on the crystallinity of the nanofibrils by the addition of amorphous components to the crystalline unit; moreover, silane surface modifications enhanced the hydrophobic character of the nanofibrils.

  1. FY 2000 survey on technical trends. Survey of technical trends on materials for heightening of performance for power generation facility use; 2000 nendo gijutsu doko nado chosa. Hatsuden shisetsuyo koseinoka zairyo ni kakawaru gijutsu doko nado chosa

    NONE

    2001-03-01

    As to high performance/high function plastic materials used in power generation facilities, technical trends were surveyed on the recycle situation and recycle R and D to study the subjects to be solved. For wire covering materials, vinyl chloride, polyethylene, rubber, etc. are used, and the recycle of resin has not been advanced. Concerning the generation of waste plastic, the existence of a lot of plastics different in characteristics makes the recycle difficult. As to the use of waste plastic as resource, the material recycle and recovery of combustion energy are being made, but only a part of the plastic is reused as chemical raw materials. Relating to the R and D of the chemical recycle technology, there are sample studies on the pyrolysis of polyolefine, dechlorination of chlorine base resins, etc. Recently, the following have been made public: proposal of depolymerization monomer based on the cyclic monomer, study of liquefaction of approximately 100% of the thermosetting resin, approach to the solvolysis by supercritical solvent. (NEDO)

  2. Report on evaluation/selection surveys on coal species, processes and others. Appendix; Tanshu process nado hyoka sentei chosa hokokusho. Furoku

    NONE

    1981-03-01

    This report, consisting of 7 chapters, summarizes literature related to liquefaction of coal. Chapter 1 describes the results of the (Project Lignite), i.e., development of the concept of two-stage liquefaction of lignite. Chapter 2 describes the COSTEAM process, which uses synthesis gas (CO-H{sub 2}) as the reducing agent and coal moisture as the hydrogen source for liquefaction of coal of low degree of carbonization, e.g., brown coal. Chapter 3 describes solubilization of coal with alcohol, where coal is reacted with ethanol and NaOH at 300 to 420 degrees C. Chapter 4 describes liquefaction of coal and production of lighter products with tetrahydroquinoline as the hydrogen donor. Chapter 5 describes low-temperature carbonization as the process for liquefying coal, in particular brown coal. Chapter 6 describes possibility of development of new liquefaction techniques for brown coal, including solvolysis for liquefaction, role, recovery and reuse of catalysts, short contact time processes, and coal pretreatment. Chapter 7 describes economic viability of the secondary hydrogenation. (NEDO)

  3. Achievement report for fiscal 1982 on Sunshine Program. Coal energy; 1982 nendo sunshine keikaku seika hokokusho. Sekitan energy

    NONE

    1982-07-01

    This research program consists of (1) the solid catalyst-aided reforming of various petroleum based oils and heavy coal oils into Solvolysis solvents and the secondary hydrogenolysis, (2) a search for pre-treatment for improvement on the sub-bituminous coal liquefaction yield, and (3) a search for measures for improvement on the brown coal liquefaction yield. Studied in this fiscal year are (1) the high-temperature short-contact time liquefaction of brown coal, (2) the role of catalyst support for selective upgrading of SRC (solvent refined coal), and (3) reforming of thermal melting feature of low rank coal by preliminary deashing at room temperature. In relation with Item (1), it is found that the dehydrogenation or reaction to carbonization of molecules involved in hydrogen donation is structure-sensitive but that thermolysis of coal is accelerated under high-temperature conditions to allow transfer hydrogen to contribute uniformly. It is deemed also that matching is excellent between hydrogen transfer and thermolysis, that the solvent dissolution level is elevated, and that the reaction short in duration inhibits consecutive polymerization reaction. These are supposed to be effective in improving on the liquefaction yield and in rendering heavy constituents lighter. In relation with Item (2), it is found that the experimentally manufactured catalysts are effective in reducing the weight of heavy constituents. In relation with Item (3), a carbonization reforming method is experimentally implemented in which the ash that affects carbonization is further removed by a pre-treatment at room temperature. (NEDO)

  4. Synergetic Effects of Alcohol/Water Mixing on the Catalytic Reductive Fractionation of Poplar Wood

    Renders, Tom; Van den Bosch, Sander; Vangeel, Thijs; Ennaert, Thijs; Koelewijn, Steven-Friso; Van den Bossche, Gil; Courtin, Christophe M.; Schutyser, Wouter; Sels, Bert F.

    2016-12-05

    One of the foremost challenges in lignocellulose conversion encompasses the integration of effective lignin valorization in current carbohydrate-oriented biorefinery schemes. Catalytic reductive fractionation (CRF) of lignocellulose offers a technology to simultaneously produce lignin-derived platform chemicals and a carbohydrate-enriched pulp via the combined action of lignin solvolysis and metal-catalyzed hydrogenolysis. Herein, the solvent (composition) plays a crucial role. In this contribution, we study the influence of alcohol/water mixtures by processing poplar sawdust in varying MeOH/water and EtOH/water blends. The results show particular effects that strongly depend on the applied water concentration. Low water concentrations enhance the removal of lignin from the biomass, while the majority of the carbohydrates are left untouched (scenario A). Contrarily, high water concentrations favor the solubilization of both hemicellulose and lignin, resulting in a more pure cellulosic residue (scenario B). For both scenarios, an evaluation was made to determine the most optimal solvent composition, based on two earlier introduced empirical efficiency descriptors (denoted LFDE and LFFE). According to these measures, 30 (A) and 70 vol % water (B) showed to be the optimal balance for both MeOH/water and EtOH/water mixtures. This successful implementation of alcohol/water mixtures allows operation under milder processing conditions in comparison to pure alcohol solvents, which is advantageous from an industrial point of view.

  5. An overview of empty fruit bunch from oil palm as feedstock for bio-oil production

    Chang, Siu Hua

    2014-01-01

    Empty fruit bunch (EFB) from oil palm is one of the potential biomass to produce biofuels like bio-oil due to its abundant supply and favorable physicochemical characteristics. Confirming the assertion, this paper presents an overview of EFB as a feedstock for bio-oil production. The fundamental characteristics of EFB in terms of proximate analysis, ultimate analysis and chemical composition, as well as the recent advances in EFB conversion processes for bio-oil production like pyrolysis and solvolysis are outlined and discussed. A comparison of properties in terms of proximate analysis, ultimate analysis and fuel properties between the bio-oil from EFB and petroleum fuel oil is included. The major challenges and future prospects towards the utilization of EFB as a useful resource for bio-oil production are also addressed. - Highlights: • Palm EFB has high heating value and low greenhouse gas emissions during combustion. • Conversion of EFB to bio-oil is mainly by fast pyrolysis without and with catalyst. • Bio-oil from EFB is lower in heating value, heavier and more acidic than fuel oil. • The viscosity of bio-oil from EFB is between those of light and heavy fuel oils. • The flash and pour points of bio-oil from EFB are close to those of light fuel oil

  6. Fast cleavage of phycocyanobilin from phycocyanin for use in food colouring.

    Roda-Serrat, Maria Cinta; Christensen, Knud Villy; El-Houri, Rime Bahij; Fretté, Xavier; Christensen, Lars Porskjær

    2018-02-01

    Phycocyanins from cyanobacteria are possible sources for new natural blue colourants. Their chromophore, phycocyanobilin (PCB), was cleaved from the apoprotein by solvolysis in alcohols and alcoholic aqueous solutions. In all cases two PCB isomers were obtained, while different solvent adducts were formed upon the use of different reagents. The reaction is believed to take place via two competing pathways, a concerted E2 elimination and a S N 2 nucleophilic substitution. Three cleavage methods were compared in terms of yield and purity: conventional reflux, sealed vessel heated in an oil bath, and microwave assisted reaction. The sealed vessel method is a new approach for fast cleavage of PCB from phycocyanin and gave at 120°C the same yield within 30min compared to 16h by the conventional reflux method (P<0.05). In addition the sealed vessel method resulted in improved purity compared to the other methods. Microwave irradiation increased product degradation. Copyright © 2017 Elsevier Ltd. All rights reserved.

  7. Solvent and ion-pairing effects on the chlorine kinetic isotope effect of t-butyl chloride

    McCord, B.R.

    1986-01-01

    The solvolysis of t-butyl chloride and 1-adamantyl chloride was measured in mixtures of aqueous 2,2,2-trifluoroethanols and in mixtures of aqueous ethanols. The KIEs for t-butyl chloride at 25 0 C in 94% TFE/water, and 60% ethanol/water (solvent mixtures with similar polarity) were 1.0097 and 1.0104 respectively. Further investigations showed a KIE of 1.0104 in 50% ethanol/water and 1.0105 in 100% ethanol while the isotope effect in the fluorinated ethanols rose from 1.0094 in 99% TFE/water to 1.0101 in 70% ethanol/water. The KIE in all these solvents were shown to be directly proportional to the nucleophilicity of the solvent and indicates nucleophilic attack on an ion pair. The similar KIE of t-butyl chloride in the ethanol/water solvents was found to support the contention that solvent polarity exerts a minimal effect on the chlorine KIE

  8. Thermochemical Conversion of Lignin for Fuels and Chemicals: A Review Conversion thermochimique de la lignine en carburants et produits chimiques : une revue

    Joffres B.

    2013-10-01

    Full Text Available Lignin is one of the biomass components potentially usable as renewable resource to produce fuels or chemicals. After separation from the lignocellulosic matrix, this macromolecule is nowadays essentially valorized by combustion in paper mills. If second generation ethanol is produced in the future from lignocellulosic biomass, some increasing reserves of lignin will be available in addition to the ones coming from the paper industry. The main thermochemical ways such as pyrolysis, solvolysis, hydrothermal conversion and hydroconversion considered for the valorization of the lignin are reviewed in this article. La lignine est une des composantes de la biomasse lignocellulosique potentiellement valorisable comme ressource renouvelable pour la production de carburants ou de produits chimiques. Après séparation de la matrice lignocellulosique, cette macromolécule est de nos jours essentiellement utilisée comme combustible dans l’industrie papetière. Outre cette filière papetière, la production d’éthanol de seconde génération à partir de la cellulose aura comme conséquence la mise à disponibilité d’encore plus grandes quantités de lignine. De nouvelles applications pourront donc être proposées pour l’utilisation de cette bio-ressource. Les différentes voies thermochimiques : pyrolyse, solvolyse, conversion hydrothermale et hydroconversion envisagées pour la valorisation de la lignine sont décrites dans cet article.

  9. Coal liquefaction committee report for fiscal 1981; 1981 nendo sekitan ekika iinkai hokokusho

    NONE

    1982-03-01

    For the assurance of smooth progress of coal technology development endeavors, the New Energy and Industrial Technology Development Organization (NEDO) has installed coal technology development committees (general committee on coal technologies, coal liquefaction committee, plant materials committee, coal type survey committee, total system committee, and coal gasification committee). The coal liquefaction committee deliberates and evaluates liquefaction technology and propels forward smoothly the efforts to develop the technology. Under the coal liquefaction committee, there are four subcommittees, which are the 1st subcommittee (primary liquefaction subcommittee), 2nd subcommittee (solid/liquid separation subcommittee), 3rd subcommittee (secondary hydrogenation subcommittee), and the 4th subcommittee (brown coal liquefaction subcommittee). The 2nd and 3rd subcommittees deal with common tasks as they were studied in fiscal 1980. The 1st subcommittee incorporates into itself the old subcommittees that respectively worked on the three liquefaction processes (the direct hydrogenation process, the solvent extraction process, and the Solvolysis process), and is designed to provide a site for information exchange. A brown coal liquefaction committee is incorporated into the coal liquefaction committee as the 4th subcommittee. This report is a compilation of the agendas of the respective subcommittees of the coal liquefaction committee. (NEDO)

  10. Kinetics of cyclopropane formation by 1,3-deoxystannylation. A kinetic isotope effect as a probe for the mechanism of neighboring group participation

    McWilliam, D.C.; Balasubramanian, T.R.; Kuivila, H.G.

    1978-01-01

    1-Aryl-3-trimethylstannyl 3,5-dinitrobenzoates, Me 3 SnCH 2 CH 2 CHAr(ODNB), 4H, undergo solvolysis in 2,2,2-trifluoroethanol to form arylcyclopropanes and trimethylstannyl dinitrobenzoate. The rates for nine substituents on Ar are correlated by sigma + with a rho value of -3.63 at 100 0 C. The rates for a series of model compounds, Me 3 CCH 2 CH 2 CHAr(ODNB), 5H (six substituents), are also correlated by sigma + with a rho value of -4.90. In each case the rate for a given 4H is greater than that for the corresponding 5H. The Winstein-Grunwald m values for 4H and 5H in aqueous acetic acid at 100 0 C are 0.41 and 0.46, respectively. Measurements of the rates of solvolyses in trifluoroethanol of the 2.2-d 2 analogues of 4H and 5H revealed kinetic isotope effects of 0.94 and 1.08, respectively. These results are taken as evidence that the mechanism for the rate acceleration observed in the 4H series is due to direct participation of the C--Sn sigma electrons in the transition state of the rate-determining step of the 1,3-elimination reaction

  11. Stereoinversion of tertiary alcohols to tertiary-alkyl isonitriles and amines.

    Pronin, Sergey V; Reiher, Christopher A; Shenvi, Ryan A

    2013-09-12

    The SN2 reaction (bimolecular nucleophilic substitution) is a well-known chemical transformation that can be used to join two smaller molecules together into a larger molecule or to exchange one functional group for another. The SN2 reaction proceeds in a very predictable manner: substitution occurs with inversion of stereochemistry, resulting from the 'backside attack' of the electrophilic carbon by the nucleophile. A significant limitation of the SN2 reaction is its intolerance for tertiary carbon atoms: whereas primary and secondary alcohols are viable precursor substrates, tertiary alcohols and their derivatives usually either fail to react or produce stereochemical mixtures of products. Here we report the stereochemical inversion of chiral tertiary alcohols with a nitrogenous nucleophile facilitated by a Lewis-acid-catalysed solvolysis. The method is chemoselective against secondary and primary alcohols, thereby complementing the selectivity of the SN2 reaction. Furthermore, this method for carbon-nitrogen bond formation mimics a putative biosynthetic step in the synthesis of marine terpenoids and enables their preparation from the corresponding terrestrial terpenes. We expect that the general attributes of the methodology will allow chiral tertiary alcohols to be considered viable substrates for stereoinversion reactions.

  12. Fluoride Bridges as Structure-Directing Motifs in 3d-4f Cluster Chemistry

    Birk, Torben; Pedersen, Kasper; Thuesen, Christian Aa.

    2012-01-01

    The use of kinetically robust chromium(III) fluorido complexes as synthons for mixed 3d-4f clusters is reported. The tendency toward linear {CrIII–F–LnIII} units dictates the cluster topology. Specifically, we show that reaction of cis-[CrIIIF2(NN)2]NO3 (NN = 1,10-phenanthroline (“phen”) or 2......-nuclear complex and fac-[CrIIIF3L′], with L′ = 1,1,1-tris-((methylamino)methylethane) (“Me3tame”), reacts with [Ln(hfac)3(H2O)2] (hfacH = 1,1,1,5,5,5-hexafluoroacetylacetone) to yield an isostructural series of {Ln3Cr2} (10–14) trigonal bipyramids with no central ligand. The formation of the latter is accompanied...... by a partial solvolysis of the Cr(III) precursor but without formation of insoluble LnF3. The magnetic properties of the gadolinium containing clusters allow quantification of fluoride-mediated, antiferromagnetic Gd–Cr exchange interactions of magnitude between 0.14 cm–1 and 0.71 cm–1 (Ĥ = J12Ŝ1·Ŝ2...

  13. Report on evaluation/selection surveys on coal species, processes and others; Tanshu process nado hyoka sentei chosa hokokusho

    NONE

    1981-03-01

    This program analyzes the applicable coal species centered by Australia's Victoria brown coal and Chinese coal, which are promising alternative fuel sources for Japan for their reserves, prices, availability, suitability for liquefaction, etc, in order to clarify the possible problems, and commercialize the liquefaction techniques in the early stage. This report consists of 6 chapters. Chapter 1 describes development situations of brown coal, specifically for Australia's Victoria brown coal and Chinese coal. Chapter 2 describes characteristics of the reactions involved in the brown coal liquefaction. Chapter 3 describes current status of various liquefaction processes (solvolysis, solvent extraction, direct hydrogenation and C-SRC) under development in Japan, and problems involved in their future developments. Chapter 4 describes current status of the elementary techniques, e.g., those for slurry pretreatment (e.g., dehydration and crushing), solid/liquid separation, secondary hydrogenation, product upgrading and gasification. Chapter 5 describes the related techniques, and Chapter 6 discusses the demonstration survey results of de-ashing, primary/secondary hydrogenation, and dehydration of brown coal. (NEDO)

  14. Report on evaluation/selection surveys on coal species, processes and others; Tanshu process nado hyoka sentei chosa hokokusho

    NONE

    1981-03-01

    This program analyzes the applicable coal species centered by Australia's Victoria brown coal and Chinese coal, which are promising alternative fuel sources for Japan for their reserves, prices, availability, suitability for liquefaction, etc, in order to clarify the possible problems, and commercialize the liquefaction techniques in the early stage. This report consists of 6 chapters. Chapter 1 describes development situations of brown coal, specifically for Australia's Victoria brown coal and Chinese coal. Chapter 2 describes characteristics of the reactions involved in the brown coal liquefaction. Chapter 3 describes current status of various liquefaction processes (solvolysis, solvent extraction, direct hydrogenation and C-SRC) under development in Japan, and problems involved in their future developments. Chapter 4 describes current status of the elementary techniques, e.g., those for slurry pretreatment (e.g., dehydration and crushing), solid/liquid separation, secondary hydrogenation, product upgrading and gasification. Chapter 5 describes the related techniques, and Chapter 6 discusses the demonstration survey results of de-ashing, primary/secondary hydrogenation, and dehydration of brown coal. (NEDO)

  15. Hydrotreatment of solvolytically liquefied lignocellulosic biomass over NiMo/Al2O3 catalyst: Reaction mechanism, hydrodeoxygenation kinetics and mass transfer model based on FTIR

    Grilc, M.; Likozar, B.; Levec, J.

    2014-01-01

    Raw residual wood biomass, containing cellulose, hemicellulose and lignin, was liquefied at low temperature by ultrasound-assisted solvolysis and acidolysis by glycerol, diethylene glycol and p-toluenesulfonic acid. Liquefied biomass was consequently upgraded by hydrotreatment utilizing heterogeneous catalysis over NiMo/Al 2 O 3 bifunctional catalyst. Effects of temperature (200−350 °C), heating rate (2.5–10.0 K min −1 ), hydrogen/nitrogen pressure (2−8 MPa), mixing (250−1000 min −1 ), hydrogen donor solvent (tetralin) and catalyst contents on deoxygenation were established. Reactions of liquefaction products, such as levulinic acid, were quantified based on their functional groups by Fourier transform infrared spectroscopy, whereas catalyst was examined by scanning electron microscopy, energy-dispersive X-ray spectroscopy (EDX) and X-ray diffraction analysis (XRD). Chemical kinetics of hydrodeoxygenation (HDO), decarbonylation and decarboxylation were determined by originally developed lumped model, based on reaction mechanisms and pathways, while the external mass transfer resistance proved to be negligible under the applied hydrodynamic conditions. The presence of hydrocracking reactions was confirmed by a decrease in product viscosity, and the upgrade for energetic or fuel applications by measurements of calorific value. - Highlights: • Liquefaction of waste lignocellulosic biomass with glycerol at low temperature. • Hydrotreatment, hydrocracking and hydrodeoxygenation of liquefied waste biomass. • Deoxygenation using heterogeneous catalysis over NiMo/Al 2 O 3 bifunctional catalyst. • Proposal of reaction mechanism; chemical kinetics and mass transfer considerations. • Effect of temperature, heating rate, pressure, mixing, solvent and catalyst content

  16. Experimental and Kinetic Study on Lignin Depolymerization in Water/Formic Acid System

    Qi Wang

    2017-10-01

    Full Text Available Microwave-assisted depolymerization of black-liquor lignin in formic acid was studied, concentrating on the yield of liquid fractions as bio-oil 1 (mainly aromatic monomers and bio-oil 2 (mainly aromatic oligomers and the distribution of the specific compositions. Bio-oil 1 (9.69% and bio-oil 2 (54.39% achieved their maximum yields under 160 °C with the reaction time of 30 min. The chemical compositions of bio-oil 1 and bio-oil 2 were respectively identified by means of Gas Chromatography-Mass Spectrometer (GC-MS and Matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS. Ethanone, 1-(4-hydroxy-3-methoxyphenyl and Ethanone, 1-(4-hydrox-3,5-dimethoxyphenyl were evidenced to be the two prominent compounds in bio-oil 1. Production of aromatic oligomers with the molecular weight of 328, 342, 358, 378, 394, 424 and 454 identified by MALDI-TOF MS was substantially tuned with the reaction temperature. A two-separate-stage kinetic model was proposed to describe the acidic solvolysis of lignin assisted by microwave heating, where the first stage is dominated by the depolyerization of lignin to monomers and oligomers with the activation energy of 40.27 kJ·mol−1, and the second stage with the activation energy of 49.18 kJ·mol−1 is mainly ascribed to the repolymerization of first-stage produced compounds.

  17. Reductive Catalytic Fractionation of Corn Stover Lignin

    Anderson, Eric M.; Katahira, Rui; Reed, Michelle; Resch, Michael G.; Karp, Eric M.; Beckham, Gregg T.; Román-Leshkov, Yuriy

    2016-12-05

    that soluble oligomers are formed via solvolysis, followed by further fragmentation on the catalyst surface via hydrogenolysis. Overall, the results show that clear trade-offs exist between the levels of lignin extraction, monomer yields, and carbohydrate retention in the residual solids for different RCF conditions of corn stover.

  18. Structure elucidation of the O-specific polysaccharide by NMR spectroscopy and selective cleavage and genetic characterization of the O-antigen of Escherichia albertii O5.

    Naumenko, Olesya I; Zheng, Han; Wang, Jianping; Senchenkova, Sof'ya N; Wang, Hong; Shashkov, Alexander S; Chizhov, Alexander O; Li, Qun; Knirel, Yuriy A; Xiong, Yanwen

    2018-03-02

    The O-specific polysaccharide (O-antigen) was obtained by mild acid degradation of the lipopolysaccharide of Escherichia albertii O5 (strain T150248) and studied by sugar analysis, selective cleavages of glycosidic linkages, and 1D and 2D 1 H and 13 C NMR spectroscopy. Partial solvolysis with anh (anhydrous) CF 3 CO 2 H and hydrolysis with 0.05 M CF 3 CO 2 H cleaved predominantly the glycosidic linkage of β-GalpNAc or β-Galf, respectively, whereas the linkages of α-GlcpNAc and β-Galp were stable. Mixtures of the corresponding tri- and tetra-saccharides thus obtained were studied by NMR spectroscopy and high-resolution ESI MS. The following new structure was established for the tetrasaccharide repeat (O-unit) of the O-polysaccharide: →4)-α-d-GlcpNAc-(1 → 4)-β-d-Galp6Ac-(1 → 6)-β-d-Galf-(1 → 3)-β-d-GalpNAc-(1→where the degree of O-acetylation of d-Galp is ∼70%. The O-polysaccharide studied has a β-d-Galp-(1 → 6)-β-d-Galf-(1 → 3)-β-d-GalpNAc trisaccharide fragment in common with the O-polysaccharides of E. albertii O7, Escherichia coli O124 and O164, and Shigella dysenteriae type 3 studied earlier. The orf5-7 in the O-antigen gene cluster of E. albertii O5 are 47%, 78%, and 75% identical on the amino acid level to genes for predicted enzymes of E. albertii O7, including Galp-transferase wfeS, UDP-d-Galp mutase glf, and Galf-transferase wfeT, respectively, which are putatively involved with the synthesis of the shared trisaccharide fragment of the O-polysaccharides. The occurrence upstream of the O-antigen gene cluster of a 4-epimerase gene gnu for conversion of undecaprenyl diphosphate-linked d-GlcNAc (UndPP-d-GlcNAc) into UndPP-d-GalNAc indicates that d-GalNAc is the first monosaccharide of the O-unit, and hence the O-units are interlinked in the O-polysaccharide of E. albertii O5 by the β-d-GalpNAc-(1 → 4)-α-d-GlcpNAc linkage. Copyright © 2017. Published by Elsevier Ltd.

  19. Analyse géochimique de la matiére organique extraite des roches sédimentaires. IV. Extraction des roches en faible quantités Geochemical Analysis of Organic Matter Extracted from Sedimentary Rocks Iv. Exraction from Small Amounts of Rock

    Monin J. C.

    2006-11-01

    extraction medium. The nature of the solvent is not critical provided that a very poor solvent for hydrocabbues is not chosen. Extractability actually depends more on the desorbing power vis-à-vis the rock thon the solving power. For resins and asphaltenes, interpreting the results is a delicote job because there is no clearcut boundary between simply dissolved products, solvolysis products and neoformation products produced by solvent/organic motter/mineral motter interaction. Hence there is no ultimately recommendable extraction procedure. Everything depends on the analytical requirements as well as on laboratory practices. The procedure retained et Institut Français du Pétrole (IFP is a beaker extraction process with magnetic stirring for 20 min in chloroform at 50 'C (approximately. The procedure for evaporation of the solvent and recovery of the extract is also described and should be studied carefully on account of the small amounts.