The reverse micelle catalyst preparation method has been used to prepare catalysts on four supports: magnesium oxide, carbon, alumina- titania and steamed Y zeolite. These catalysts were not as active as a reference catalyst prepared during previous contracts to Union Carbide Corp. This catalyst was supported on steamed Y zerolite support and was impregnated by a pore-filling method using a nonaqueous solvent. Additional catalysts were prepared via pore- filling impregnation of steamed Y zeolites. These catalysts had levels of cobalt two to three and a half times as high as the original Union Carbide catalyst. On a catalyst volume basis they were much more active than the previous catalyst; on an atom by atom basis the cobalt was about of the same activity, i.e., the high cobalt ...
This quarterly report, for the period April 1-June 30, 1982, summarizes Sandia's activities in coal liquefaction process research. The overall objectives of the program are to understand the mechanisms and determine the role of catalysts in the direct conversion of coal to liquids. Primary emphasis is being given to the Integrated Two-Stage Liquefaction (ITSL) process. Specific tasks include: short-contact time coal liquefaction, mineral matter effects and catalyst studies. During this period, work was done on: the characteristics of a Liquefaction (ITSL) facility at New Brunswick, NJ; the kinetics of hydrogenation and dehydrogenation of pyrene and dihydropyrenes in batch microreactors; the impact of coal cleaning on the effectiveness of two types of slurry phase catalysts; the deactivation of aged catalyst samples obtained from the H-Coal PDU; and a ...
Objectives of the program are to understand the mechanisms of coal liquefaction, to determine the role of catalysts in the direct conversion of coal to liquids, to determine the mechanism of catalyst deactivation and to explore slurry phase catalyst systems. Specific projects include: short-contact time coal liquefaction, mineral matter effects and catalyst studies. During this period, work was performed on: (1) the stability, at reaction temperature, of a recycle solvent obtained from the Lummus Two Stage Liquefaction facility, (2) reactions of preasphaltenes and asphaltenes prepared under various reaction severities, (3) the evaluation of the catalyst level detector installed at the H-Coal facility, (4) the characterization of oil soluble metal compounds with respect to hydrogenation activity, and (5) characterization, deactivation and regeneration of ...
This quarterly report for the period April through June 1984 summarizes activities in Sandia National Laboratories' continuing program of coal liquefaction research. The primary goals are to: explore novel catalytic concepts and materials for conversion of coal to liquid fuels; determine the effects of process variables on catalyst deactivation; determine the effects of coal structure and solvent properties on low temperature dissolution; study the kinetics and catalysis of hydrogen transfer reactions; develop an understanding of slurry gelling phenomena; and provide a technical assessment of coal liquefaction processes. During this period, work was performed on: analysis of catalyst samples from Wilsonville Run 246; catalyst presulfiding; catalyst activity testing using pyrene as a chemical probe; catalyst deactivation using a high-pressure model ...
Cobalt supported on Beta zeolite catalysts were prepared by impregnation of metal salts in aqueous solution and were tested for the Fischer Tropsch reaction. The support consisted of a Beta zeolite composed by crystallites of nanometric dimensions and a SiO2/Al2O3 molar ratio of about 50. This support was impregnated with Co(NO3)2 aqueous solution using different metal loads of 7.5, 10, 15 and 20wt% Co. These materials were characterized by X-ray diffraction (XRD), high resolution transmission electron microscopy (HRTEM), N2 adsorption (BET), thermal programmed reduction (TPR) and FTIR of adsorbed pyridine (i.e., surface acid sites distribution). All the catalysts showed a significant catalytic activity for the F-T reaction from synthesis gas (CO+2H2), in a continuous fixed bed reactor sys...
In October 1980, Air Products and Chemicals, Inc. began a three year contract with the DOE: Catalyst and Reactor Development for a Liquid Phase Fischer-Tropsch Process. The program contains four major tasks: (1) Project Work Plan, (2) Slurry Catalyst Development, (3) Slurry Reactor Design Studies, and (4) Pilot Facility Design. This report describes work on Tasks 2 and 3 carried out in the third quarter of the contract. In Task 2, the computerized search of the Fischer-Tropsch literature was continued, and improvements were made in data processing programs. Shakedown tests were completed on the first 300 ml slurry reactor, and construction of the second and third reactors began. Five modified conventional slurry catalysts were prepared, and two batches were tested in the gas phase giving information on selectivity as a function of composition and activation. Four supported cluster ...
A laser pyrolysis technique has been used to produce ultrafine particles of iron carbide with diameters ranging from 2 to 20 nm. Catalysis using iron carbide was investigated in the liquefaction of Wyodak subbituminous coal; yields were determined. A study was carried out to examine the possibility of using an ultrasonic extraction technique as a rapid method of product work-up of samples following pretreatment or liquefaction experiments. A similar study had shown that extraction of coal-derived products by an ultrasonic method was rapid and gave yields and product distributions comparable to those obtained by Soxhlet extraction. On another project, three different types of supported catalysts were used to test activity for the combined water-gas shift hydrogenation of a synthetic donor solvent. The three catalysts tested were: (1) Alumina supported NiMo catalyst-Shell 324m; (2) Bulk hydrous TiO NiMo ...
This quarterly report for the period July through September 1984 summarizes activities in Sandia National Laboratories' continuing program of coal liquefaction research. The primary goals are to: explore novel catalytic concepts and materials for conversion of coal to liquid fuels; determine the effects of process variables on catalyst deactivation; determine the effects of coal structure and solvent properties on low temperature dissolution; study the kinetics and catalysis of hydrogen transfer reactions; develop an understanding of slurry gelling phenomena; and provide a technical assessment of coal liquefaction processes. During this period, work was performed on: the rheology of Illinois No. 6 coal in hydrogenated creosote oil; dissolution chemistry of subbituminous coal; pyrite catalysis; liquefaction of Illinois No. 6 coal in indole; characterization and activity testing of catalyst samples from Wilsonville ...
Since fuel oil meeting the requirements of current petroleum products can be produced by SASOL F-T synthetic process, the manufacturing process of hydrocarbon fuel oil from the coal-derived synthesis gas, downstream processes are being successively investigated. Mobile M-gasoline, MTG, process which produces gasoline from the natural gas-derived synthesis gas through methanol went into commercial operation in New Zealand in 1986. Although the gasoline suffices the quality of commercial gasoline by both fixed bed and fluidized bed systems, the price and service life of catalyst and control of by-product durene must be improved. Any STG processes have not been completed yet and the yield and quality of gasoline are inferior to those of gasoline produced by the MTG process. Applying two-stage process, the STG process will be more economically effective.(21 refs, 4 figs, 10 tabs)
The overall objective of this project is the three phase development of an Early Entrance Coproduction Plant (EECP) which uses petroleum coke to produce at least one product from at least two of the following three categories: (1) electric power (or heat), (2) fuels, and (3) chemicals using ChevronTexaco's proprietary gasification technology. The objective of Phase I is to determine the feasibility and define the concept for the EECP located at a specific site; develop a Research, Development, and Testing (RD&T) Plan to mitigate technical risks and barriers; and prepare a Preliminary Project Financing Plan. The objective of Phase II is to implement the work as outlined in the Phase I RD&T Plan to enhance the development and commercial acceptance of coproduction technology. The objective of Phase III is to develop an engineering design package and a financing and testing plan for an EECP located at a specific site. The project's intended result is to provide ...
In the course of observing by means of Auger spectroscopy graphite gasification reactions catalyzed by metals, it has been found that in the presence of hydrogen, nickel appears to diffuse from the surface into the bulk of the graphite. When potassium is deposited on graphite, it is volatilized above 400/sup 0/C. Surprisingly the production of methane and carbon dioxide from the reaction of graphite and steam was catalyzed by potassium at as low a temperature as 250/sup 0/C. It has been shown that literature on the alkylation of benzene with synthesis gas is erroneous and that the products reported are due to Lewis acid catalyzed cracking of benzene. A novel cobalt mediated, reversible cleavage of a vinyl-hydrogen bond has been discovered. All products from the thermal decomposition of tetralin have been identified. The stereochemistry of cis-1, 2 dihydrotetralin was determined. In the utilization of the water gas shift reaction as a reducing agent for model coal compounds it has been ...
Results of research programs in coal liquefaction are presented. Areas of research include: desulfurization by bioprocessing; characterization of coal liquefaction processes by XAFS spectroscopy; coprocessing of coal with heavy oil and petroleum residuals; liquefaction research in pyrolysis, catalysis and coal dissolution; novel catalysts; data base development; resource evaluation; depolymerization; solvent extraction and chromatography; correlations of liquefaction yields and coal structure. Individual projects are processed separately for the data bases. (CBS)
Research programs on coal and coal liquefaction are presented. Topics discussed are: coal science, combustion, kinetics, surface science; advanced technology projects in liquefaction; two stage liquefaction and direct liquefaction; catalysts of liquefaction; Fischer-Tropsch synthesis and thermodynamics; alternative fuels utilization; coal preparation; biodegradation; advanced combustion technology; flue gas cleanup; environmental coordination, and technology transfer. Individual projects are processed separately for the data base. (CBS)
The objectives of this project are to develop feasible synthetic routes to produce (1) 4(4{prime}-hydroxy-5{prime},6{prime},7{prime},8{prime}-tetrahydro-1{prime}-naphthylmethyl)-6-methyldibenzothiophene, and (2) a 1-hydroxynaphthalene-dibenzothiophene polymer. These compounds are thought to be representative of sulfur containing molecules in coal. The program is divided into three tasks, the first of which is a project work plan that has already been submitted. There are several possible synthetic routes to the target molecule (1). The authors are now investigating two general synthetic approaches: coupling of a dialkylated dibenzothiophene fragment with the phenol, and coupling of a monoalkylated dibenzothiophene fragment with a monoalkylated phenol fragment. This quarter they developed syntheses for the reaction fragments and conducted some preliminary coupling experiments. They found that polymerization of the fragments is a problem; however, using an acidic ...
This report presents the work performed at the Institute of Gas Technology (IGT) during the second program quarter from October 1, 1993 to December 31, 1993, under Department of Energy (DOE) Contract No. DE-AC22-93PC92114. This program has co-ordinated funding for Task 1 from IGT`s Sustaining Membership Program (SMP), while DOE is funding Tasks 2--8. Progress in all tasks are reported. The overall objective of this research project is to develop a catalytic process to convert natural gas to liquid transportation fuels. The process consists of two steps that each utilize catalysts and sulfur containing intermediates: (1) to convert natural gas to CS{sub 2} and (2) to convert CS{sub 2} to gasoline range liquids. Experimental data will be generated to demonstrate the potential of catalysts and the overall process. During this quarter, progress in the following areas has been made. An existing unit at IGT ...
As stated last quarter, we discovered potassium as an impurity in the mixed metal oxides. The potassium was probably incorporated into the solid during the coprecipitation using K{sub 2}CO{sub 3}. Currently NH{sub 4}OH is being used as the precipitating base. We have discovered that the precipitation agent influences the surface composition of the mixed-metal oxides. Chemical analysis of the surface and bulk compositions showed significant differences in surface compositions of the K{sub 2}CO{sub 3} and NH{sub 4}OH precipitated catalysts. In TPR experiments we have discovered that the precipitating pH markedly affects the reducibility of the ZnMnCr oxides. This shows that the choice of base as well as the pH strongly affects the surface composition of the mixed metal catalysts. Additional studies are in progress in which we are studying how the precipitating agents affect the surface composition of the mixed metal oxide ...
The objectives of this contract are to conduct exploratory coal liquefaction research on modified solvents with slurry phase catalysts and on coal pretreatment. This report describes a review of the existing literature as well as currently on-going research in the areas of: (1) solvent quality effects on coal liquefaction; (2) role of heteroatoms in liquefaction of coal; (3) heteroatoms removal through solvent treatment, extraction and hydrogenation; (4) slurry phase catalysts in hydroprocessing of coal; and (5) effect of coal preparation and pretreatment on liquefaction. The review encompasses both technical papers and presentations as well as the patent literature. This report is comprised of two distinct parts. In Part I all the literature available on the effect of solvent quality, heteroatoms, heteroatoms removal, and slurry phase catalysts on coal liquefaction is incorporated. The existing literature and currently ...
Fischer-Tropsch (F-T) diesel fuel is characterized by a high cetane number, a near-zero sulphur content and a very low aromatic level. On the basis of the recorded incylinder pressures and injector needle lifts, the combustion characteristics of an unmodified single-cylinder direct-injection diesel engine operating on F-T diesel fuel are analyzed and compared with those of conventional diesel fuel operation. The results show that F-T diesel fuel exhibits a slightly longer injection delay and injection duration, an average of 18.7% shorter ignition delay, and a comparable total combustion duration when compared to those of conventional diesel fuel. Meanwhile, F-T diesel fuel displays an average of 26.8% lower peak value of premixed burning rate and a higher peak value of diffusive burning rate. In addition, the F-T diesel engine has a slightly lower peak combustion pressure, a far ...
Objective: Evidence from adults suggests that changes in thyroid function are associated with the development of bipolar disorder (BD) and severe mood dysregulation. A dysregulation profile based on the Child Behavior Checklist (CBCL-DP) describes a phenotype with severe mood problems in youth. The present study investigated whether altered thyroid functioning in youths is associated with the severe mood dysregulation symptoms characterized by the CBCL-DP. Methods: We analyzed the thyroid function data from 262 children and adolescents (n=262 for serum TSH, n=148 for free triiodothyronine [fT3] and n=153 for free thyroxine [fT4]) with their CBCL-DP composite score. We created and compared high CBCL-DP and low CBCL-DP subgroups with regard to their serum TSH, fT3 and fT4 concentrations as w...
In YbPd_2Si_2, the valence of Yb is very close to 3+. Ge substitution of Si induces a negative pressure effect and the valence of Yb decreases. For the low Ge concentrations studied, the spin fluctuation temperature T_s_f increases and #chi#4f, the Yb derived 4f susceptibility, obeys the scaling law #chi#4f(T)=F(T/T_s_f). (orig.).
The H-Coal ebullated bed reactor contains at least four discrete components: gas, liquid, catalyst, and unconverted coal and ash. Because of the complexity created by these four components, it is desirable to understand the fluid dynamics of the system. The objective of this program is to establish the dependence of the ebullated bed fluid dynamics on process parameters. This will permit improved control of the ebullated bed reactor. Progress has been made in the study undertaken for defining the hydrodynamic properties of gas/liquid/solid systems as related to the H-Coal process. The literature search was completed, and a report will be issued shortly. Design and construction of the fluid dynamics unit proceeded as planned. Unit completion is scheduled for May 1, 1978.
All first-stage experimental tests were completed for Task 4 (and the Contract). The first-stage one-liter autoclave tests that were made were duplicates of Run 41-LA. The conditions used were chosen last quarter to reduce the cost of the first-stage of the process from those used at the conclusion of Task 3. Filtration and second-stage tests were made using the products of the first-stage tests. Post-second-stage filtration, tested as an alternative to interstage (pre-second- stage) filtration, resulted in low filtration rates. Different catalyst loadings and type and residence time for second-stage hydrotreating were explored. Longer residence times did not result in significantly more resid conversion. Higher catalyst loadings were more effective in converting the resid at the same residence time. The material and elemental balances for the first-stage were completed. The material and elemental balances for the ...
During this reporting period four direct coal liquefaction experiments have been completed and a fifth is underway. These experiments have produced conversion and selectivity data on samples of Utah coal slurried in tetralin and catalyzed using iron-titanium hydride. Hydrogen loading of the alloy, catalyst particle size, coal particle size, operating temperatures for alloy addition and liquefaction without the catalysts present, have all been studied during these four experiments. Conversions of 61% DAF in 30 min have been recorded at 485/sup 0/F and 520 psia. The fifth run using the same coal at a reduced particle size has begun, after which we will move to samples of Kentucky and Alabama coals. Equipment manufacture, delivery, and installation delays, totaling over 6 months, greatly reduced the time available for research, making a 6 month no cost extension necessary. The extended time will permit completion of the proposed research tasks. 4 ...
Having recently discovered that polynuclear heteroaromatic nitrogen compounds can be selectively reduced only at the nitrogen containing ring, we have now turned our attention towards the cleavage of the carbon nitrogen bonds in this reduced ring. Highlights for this reporting period are: (1) Studies with the 50% nickel oxide catalyst clearly show that 1,2,3,4-tetrahydroquinoline(THQ) provides approximately 20% more liquid product that does quinoline. Thus a first step selective hydrogenation to 1,2,3,4-THQ would enhance the overall HDN reaction to provide a more substantial conversion to substituted benzene and aniline derivatives. (2) The dramatic effect of the nitrogen atom is to inhibit aromatic ring hydrogenation and, to some extent, carbon-carbon bond hydrogenolysis reactivity. This is shown with proplybenzene as the substrate, where only methane gas is produced in the HDN reaction with the 50% nickel oxide catalyst. (3) The HDN reaction ...
Kusy,. R. P. and. Corneliussen,. R. D.,. Polym. Eng. Sci.,. 15,. 1975 pp. 107. DeAraujo,. F. T. and. Rostenberg,. H. M.,. Jour. Phys.,. Sec. D,. Appl. ...
The first quarter 1982 report summarizes the operating and test data obtained at the six ton per day Advanced Coal Liquefaction Research and Development Facility in Wilsonville, Alabama. The Wilsonville R and D Facility was in operation 52% of the period with scheduled shutdowns accounting for 33% of the downtime. Illinois 6 coal from the Burning Star No. 2 mine was processed during Run 236. The three process units of the Wilsonville facility were operated in a non-integrated mode to evaluate process parameters and to test equipment and operating modifications. Data were obtained in the following areas: In the SRC Unit: operation at low severity reaction conditions for single stage liquefaction with a high LSRC recycle rate using Illinois 6 coal; process solvent activity control; and preliminary feeding tests with hydrotreated SRC as a replacement for LSRC in the process solvent. In the CSD Unit: operation with T102 Vacuum Column bottoms produced at low severity ...
New furnaces were built based on fused silica with NiChrome heating elements custom-wound on alumina ceramic to self-compensate for induced magnetic fields during operation. During tests these furnaces failed due to thermal stresses caused by the high temperature cement used to hold the alumina ceramic in place. As a third solution pieces of boron nitride have been procured from which new furnace bodies will be machined during the third quarter. In order to increase the in-house capacity for machining ceramic parts a small lathe was ordered. The implementation of the LabView data acquisition software from National Instruments, Inc. took more time than anticipated and is still not completed. Major difficulties had to be overcome during the integration of the separate positive and negative high voltage supplies ({plus_minus}1000V). It became apparent that a custom-designed switch had to be installed to safeguard the data acquisition modules and the Apple Macintosh ...
Five barrels of a Wilsonville process derived solvent (V-1074) from Black Thunder coal were obtained. This material boils within the preferred gas oil range, is more aromatic than previous solvents, and will therefore be used for the bench unit studies. Several repeat runs were performed in the autoclave to confirm the results of the matrix study. In addition, runs were carried out with different catalysts, with agglomerates and with the V-1074 solvent. The results of the autoclave runs were analyzed with respect to coal conversion, CO conversion, oil yield, hydrogen consumption and oxygen removal. It was concluded that the best operating conditions for the first stage operation was a temperature of at least 390{degrees}C, residence time of at least 30 minutes, cold CO pressure of at least 600 psig and potassium carbonate catalyst (2% wt on total feed). The data also indicated however, that the coal conversion goes through a maximum, and too ...
Assessments of the hardening and embrittlement of pressure vessel steels and welds as a function of neutron dose use trend curves derived from surveillance programs and accelerated irradiation data. A temperature dependent factor is incorporated for assessing vessel locations operating at different temperatures. As hardening and embrittlement arise from the sum of matrix damage and copper impurity precipitation, the influence of irradiation temperature on each process needs to be established. For irradiations performed below #approx# 300 C recent data shows that the dose-dependent growth of copper precipitates ceases at a mean diameter of about 2 nm that also corresponds to peak hardening and embrittlement by copper. For doses beyond this peak copper dose the property-dependence on irradiation temperature can be identified with that of matrix damage alone. An analysis of several experiments on plate steels, performed at differing irradiation temperatures, has permitted the temperature ...
A transition from petroleum~derived jet fuels to blends with Fischer-Tropsch (F~T) fuels, and ultimately fully synthetic hydro-isomerized F-T fuels has raised concern about the fate of plasticizers in nitrile-butadiene rubber a-rings that are contacted by the fuels as this transition occurs. The partitioning of plasticizers and fuel molecules between nitrile a-rings and petroleum-derived, synthetic, and additized-synthetic jet fuels has been measured. Thermal desorption of o-rings soaked in the various jet fuels followed by gas chromatographic analysis with a mass spectrometric detector showed many of the plasticizer and stabilizer compounds were removed from the o-rings regardless of the contact fuel. Fuel molecules were observed to migrate into the o-rings for the petroleum-derived fuel as did both the fuel and additive for a synthetic F-T jet fuel additized with benzyl alcohol, but less for the unadditized synthetic ...
A process is described for covering methane to a higher order hydrocarbon comprising contacting a gaseous reactant consisting of methane with a phosphate-containing catalyst for a sufficient period of time and at an effective temperature to provide the phosphate-containing catalyst consisting essentially of the higher order hydrocarbon. The catalyst is represented by a formula.
A procedure based on electrophoretic deposition (EPD) was developed to coat metal plates with powder catalysts. The method was tested on stainless-steel plates with three Ni-based catalysts for the steam reforming of ethanol. The catalysts (Ni/La2O3/g-Al2O3) contained 15% Ni and 8% La, and were prepared using three types of g-alumina with different textural properties. The powder catalysts were suspended in isopropanol, and EPD deposition was performed with a voltage of 100V and a distance between electrodes of 2cm. Deposition time was varied between 3 and 7min, which gave a thickness of the catalyst layer from around 30 to 100mm. The morphology of the catalyst layer was dependent on the textural characteristics of the g-Al2O3 used to prepare the catalyst. The activity of the catalyst plat...
Very high cobalt catalysts have been prepared on steamed and acid-washed y zeolite. These catalysts are very active. Some of them have proven to be very stable. Additionally, if provisions are made to control the temperature build up on the catalyst bed, low methane selectivities result. Additional work is indicated, for instance, perhaps even higher activity catalysts can result from higher levels of cobalt or changes in the catalyst preparation procedure. Since the issue of whether small amounts of ruthenium can promote the catalyst is not completely resolved, catalyst preparation procedure experiments should continue with ruthenium vs. ruthenium-free catalysts. For instance, different methods of impregnation and/or activation should be investigated.
A phosphorus-containing low alkali metal content zeolitic catalyst made from a clay starting material is provided. The catalyst is obtained by contacting a partially cation exchanged calcined zeolite-containing catalyst with a dihydrogen phosphate anion or a dihydrogen phosphite anion. A hydrocarbon catalytic cracking process utilizing the phosphorus-containing catalyst is also provided.
A phosphorus-containing low alkali metal content zeolitic catalyst made from a clay starting material is provided. The catalyst is obtained by contacting a partially cation exchanged calcined zeolite-containing catalyst with an anion such as a dihydrogen phosphate anion or a dihydrogen phosphite anion and additionally with an ammonium salt other than a salt of an inorganic acid of phosphorus. A hydrocarbon catalytic cracking process utilizing the phosphorus-containing catalyst is also provided.
This report describes progress on the Advanced Coal Liquefaction project by the Gulf Research and Development Company's Merriam Laboratory during the months of January through March 1983. The liquefaction behavior of Illinois No. 6 coal beneficiated in various ways was studied in both single-stage recycle (SRC II) and short contact time (SCT) modes of operation. The distillate yield increased as the iron level in the feed slurry increased in both modes of operation. In the SCT mode, the conversion increased at greater depths of cleaning. In the SRC II mode, the distillate yield and conversion were much higher with deep cleaning and add-back of pyrite than with conventional cleaning. Pyrite addition resulted in a significant increase in short contact time conversion of subbituminous Belle Ayr coal in both high and low quality solvents. Solvent quality itself, however, had little effect on conversion. With Loveridge coal, the hydrocarbon gas yield and conversion decreased as the ...
In order to replace industrial cobalt and nickel and molybdenum catalysts, more economical catalysts, red muds, are used. Comparative data about the chemical, structural and thermal properties of different samples of red muds, which are important for catalytic hydrogenation, are cited. The different conditions for hydrogenation of coals in a reactor are examined.
A highly dispersed limonite catalyst was shown to have advantageous properties in a commercial liquefaction plant: it has high catalytic activity, low cost for catalyst production and abundant resources. 3 refs., 3 figs., 2 tabs.
This patent describes a catalyst composition. It consists of the catalytic oxides of iron, bismuth, molybdenum and magnesium as essential components and optionally the oxides of cobalt, nickel, phosphorus and arsenic.
This is the quarterly progress review report for Wolsung NPP 2, 3, 4 NSSS design and engineering which evaluates the performance of project and describes the project highlight, manpower loading status, design and engineering and project related meeting by...
This quarterly update contains information on the National Bioenergy Center Biochemical Platform Integration Project, R&D progress and related activities.
The deactivation rate of a resid hydrotreating catalyst is determined by a complex set of factors involving both chemical and physical changes in the catalyst structure. The various chemical changes that are associated with resid conversion involve thermal and catalytic steps of relatively large molecular weight species with the overall rates significantly affected by mass transfer limitations. The deposition of coke and the variation in the effective promoter level by the accumulation of metals deposited from the resid are the principal factors governing deactivation. The relative importance of mass transfer restrictions on activity and catalyst deactivation can be observed in studies where the average pore diameter of the catalyst has been varied. Several models have been proposed to characterize the deactivation of resid hydroprocessing catalysts. In this paper, the authors ...
Thermodynamic states encountered during combustion of Aluminum powder in Shock-Dispersed-Fuel (SDF) explosions were analyzed with the Cheetah code. Results are displayed in the Le Chatelier diagram: the locus of states of specific internal energy versus temperature. Accuracy of the results was confirmed by comparing the fuel and products curves with the heats of detonation and combustion, and species composition as measured in bomb calorimeter experiments. Results were fit with analytic functions u = f(T) suitable for specifying the thermodynamic properties required for gas-dynamic models of combustion in explosions.
The objective of this project is the development of a new class of metalloporphyrin materials used as catalsyts for use in fuel cell applications. The metalloporphyrins are excellent candidates for use as catalysts at both the anode and cathode. The catalysts reduce oxygen in 1 M potassium hydroxide, as well as in 2 M sulfuric acid. Covalent attachment to carbon supports is being investigated. The computer-aided molecular design is an iterative process, in which experimental results feed back into the design of future catalysts.
Experimental tests were performed in a continuous-flow hydrotreating unit at Pittsburgh Energy Technology Center to evaluate the performance of hydrous titanium-oxide supported (HTO) catalysts as hydrotreating catalysts for use in two-stage coal liquiefaction. Catalysts containing either a combination of CO, Ni, and Mo as the active metal components or Pd as the active metal componet were tested with representative hydrotreater feed stocks from the Wilsonville Advanced Coal Liquefaction Research and Development Facility. Catalyst performance evaluation was based on desulfurization and denitrogenation activity, the conversion of cyclohexane-insolbule material, and hydrogenation activity during 100-hour reactor runs. Results indicated that the HTO catalysts were comparable to a commercial Ni/Mo-alumina supported catalyst in the areas evaluated. 11 refs., 1 fig., 6 ...
Red mud is a by-product of bauxite processing through Bayer process. The amount of red mud generated depends largely on the type of ore used and the processing. Use of red mud as a catalyst can be a good alternative to the existing commercial catalysts. Its properties such as iron content in form of ferric oxide (Fe{sub 2}O{sub 3}), high surface area, sintering resistance, resistance to poisoning and low cost make it an attractive potential catalyst for many reactions. Besides red mud, ferric ion sludge from wastewater treatment plant has also been studied for its catalytic properties, mainly due to its ferric oxide constituent. This paper reviews the studies on red mud as a catalyst. The catalyst characteristics, reaction mechanisms involved and performance are examined and compared with iron oxide catalyst and commercial catalysts. ...
The effect of method of sulfur addition on the hydrocracking activity of coal liquefaction catalysts was investigated using a high-pressure differential thermal analyser. The three methods of sulfur addition were: 1) physical mixing of 10 wt% elemental sulfur with red mud; 2) pre-sulfidation of red mud with hydrogen sulfide; 3) use of reagent grade pyrite. The pre-sulfided catalyst was slightly less active than the catalyst prepared by physical mixing, and both of these were changed to pyrrhotite in the course of use. Although the pyrite catalyst exhibited activity at markedly lower temperatures than those required for the other two catalysts, conversions were lower than had been expected. This is thought to be due to a different catalytic mechanism being involved. 13 references.
The Quarterly Coal Report (QCR) provides comprehensive information about US coal production, distribution, exports, imports, receipts, prices, consumption, and stocks to a wide audience, including Congress, Federal and State agencies, the coal industry, and the general public. Coke production, consumption, distribution, imports, and exports data are also provided. The data presented in the QCR are collected and published by the Energy Information Administration (EIA) to fulfill data collection and dissemination responsibilities. This report presents detailed quarterly data for october through December 1997 and aggregated quarterly historical data for 1991 through the third quarter of 1997. Appendix A displays, from 1991 on, detailed quarterly historical coal imports data, as specified in Section 202 of the energy Policy and Conservation Amendments Act of 1985 (Public Law 99-58). ...
The research has involved the characterization of catalyst acidity, [sup 2]D NMR studies of Bronsted acid sites, and kinetic, calorimetric, and spectroscopic studies of methylamine synthesis and related reactions over acid catalysts. Approach of this work was to explore quantitative correlations between factors that control the generation, type, strength, and catalytic properties of acid sites on zeolite catalysts. Microcalorimetry, thermogravimetric analysis, IR spectroscopy, and NMR spectroscopy have provided information about the nature and strength of acid sites in zeolites. This was vital in understanding the catalytic cycles involved in methylamine synthesis and related reactions over zeolite catalysts.
It has been discovered that when Taiheiyo coal pulverized to 200 mesh or smaller is dispersed in naphthalene, a non-hydrogen-donor solvent, and reacted under hydrogen pressure in the presence of a red mud/sulfur catalyst, the catalyst exhibits activity in the regeneration of hydrogen donor solvents which have been hydrogen-depleted in the course of coal liquefaction. It is already known that inorganic matter contained in coal acts as a catalyst in liquefaction. This suggests that the reported effect of the red mud/sulfur catalyst is due to the iron oxide reacting with the sulfur and forming pyrrhotite. 22 refs., 6 figs., 1 tab.
Pt-based ternary catalysts have been proposed as electrode materials for low temperature fuel cells. Pt-Ru-based ternary catalysts were tested as anode materials with improved CO tolerance or enhanced activity for methanol or ethanol oxidation. Ternary catalysts based on platinum alloyed with first row transition metals were tested as cathode materials with improved activity for the oxygen reduction. This paper presents an overview of the preparation methods and structural characteristics of these ternary catalysts. (author)
The effect of two iron catalysts, red mud and CGS S-G, as well as Co-Mo/Al/sub 2/O/sub 3/ and Ni-Mo/Al/sub 2/O/sub 3/ commercial catalysts on the composition of oil derived from the liquefaction of Japanese subbituminous coal have been investigated comparatively by conventional autoclave experiments at 440 and 450C under initial hydrogen pressure of 85kg/cm/sup 2/ . G with tetralin to coal weight ratio of 3. From the results obtained at 450C, total conversion and the yield of gas revealed almost same level with four catalysts, but the oil product from molybdenum catalysts showed higher yield than that from iron catalysts. CGS S-G catalyst also showed higher yield of oil product than red mud catalyst. Reaction behavior of two iron catalysts were also tested by solvent recycle mode experiments.
The indirect conversion of coal to liquid hydrocarbons via steam gasification followed by synthesis gas (CO/H/sub 2/) chemistry has been the subject of intensive study for a number of decades. A key technological challenge facing researchers in this area is control over the product distribution during the hydrocarbon synthesis step. In the case of iron Fischer-Tropsch catalysts, it has been known that the addition of alkali to the metal catalyst has a significant impact on the product distribution. Iron catalysts treated with alkali produce less methane more alkenes and higher molecular weight products. In spite of numerous investigations, the details of this promotional effect are not understood on a molecular level. To explore the role of alkali in the surface chemistry of iron catalysts, the authors have carried out a combined surface science and catalytic kinetic study of a model iron ...
The authors present the results of their investigation of the effect of phosphorus compounds on the activity of tungsten-containing catalysts in the oxidation of ethane. They investigated tungsten-phosphorus catalysts with different phosphorus concentrations (calculated on the basis of P/sub 2/O/sub 5/). The catalysts were prepared by heat decomposition of the starting compounds at 750/sup 0/C for 4 h. As their starting compounds, they used two types of materials: heteropoly acids mixtures of monosubstituted ammonium phosphoric and tungstic acids. The specific surface area of the catalysts was determined using the nitrogen desorption method. The x-ray phase analysis was carried out using a DRON-1.5 diffractometer. The catalytic activity was determined using the impulse method in a reactor with a vibrofluidized catalyst layer.
Co catalysts, obtained from a layered double Co?Zn?Al hydroxide, are highly active and stable towards the hydrogenolysis of glycerol to 1,2-propanediol (1,2-PDO) in aqueous media. The Co-673 catalyst, containing a CoO species, provided a glycerol conversion of 67.7% and a 1,2-PDO selectivity of 50.5%. The Co-873 catalyst comprising 16?nm Co nanoparticles gave a glycerol conversion of 70.6% and a 1,2-PDO selectivity of 57.8%. It was revealed that the CoO species in the Co-673 catalyst was readily converted to 50?nm Co particles under the glycerol hydrogenolysis conditions. The Co catalysts maintained a stable size and phase in recycling tests. Graphical Abstract
In the dehydrodesulfurization of ethanethiol at 400/sup 0/C, the activities of sodium X, Y, and A zeolites decreased in the order given as did the activities of nickel, cobalt, zinc, cadmium, copper, silver, lead, manganese, barium, calcium, sodium, and iron Y zeolite catalysts. A volcano-shape order was observed between the catalytic activity and the electronegativity of the metal ions. The changes in the activity of hydrogen Y zeolite catalyst in ethanethiol dehydrodesulfurization and cumene dealkylation by calcination agreed with the decrease in the Broensted acidity but were independent of Lewis acidity. For hydrodesulfurization of thiophene, the activities of nickel, cobalt, copper, and silver Y zeolite catalysts decreased in the order given and were greater than for a commercial hydrodesulfurization catalyst; reduced and presulfided catalysts showed selective ...
Industrial solid wastes (fly ash and red mud, a by-product of the aluminium industry) have been employed as supports for preparation of Ru-based catalysts. Physical and chemical treatments on red mud were conducted and these modified supports were also used for preparation of Ru-based catalysts. Those Ru catalysts were characterized by various techniques such as N2 adsorption, H{sub 2} adsorption, XRD, XPS, and temperature-programmed reduction (TPR), and were then tested for catalytic ammonia decomposition to hydrogen. It was found that red-mud-supported Ru catalyst exhibits higher ammonia conversion and hydrogen production than fly-ash-supported catalyst. Heat and chemical treatments of the red mud greatly improve the catalytic activity. Moreover, a combination of acid and heat treatments produces the highest catalytic conversion of ammonia. 35 refs., 4 figs., 4 tabs.
Y-zeolite supported catalysts were applied to the hydrocracking of coal-derived liquids. By the introduction of two-stage upgrading consisting of hydrotreating and hydrocracking, Wandoan coal-derived middle distillate was hydrocracked over Ni-Mo/Y-zeolite, producing a high gasoline fraction yield. Zeolite supported catalysts gave little hydrocracked compounds in the hydroprocessing of coal-derived heavy oils, even after hydrotreatment. The reaction inhibitors which seriously poison the active sites of zeolites were found to be small nitrogen-containing molecules. In the hydroprocessing of coal-derived heavy oils, zeolite supported catalysts were inferior to alumina supported catalysts. This is due to the high hydrocracking but low hydrogenation activity of zeolite supported catalysts. 22 refs., 5 figs., 11 tabs.
Catalyst deactivation during steam reforming of transportation fuels, primarily due to sulfur poisoning and carbon deposition, is a major hurdle in the commercialization of fuel cell technologies. In an attempt to better understand the phenomena, a previously formulated multi-component (Ni, Pd, Rh) catalyst supported on g-Al2O3 was studied under steam reforming of Jet A spiked with thiophene to achieve a total sulfur content of 1000ppm by weight. Analysis of fresh catalysts showed the presence of two groups of active metal particles, primarily distinguished by their size and composition; small particles (1-5nm) largely comprised of Rh and large particles (10-20nm) that were predominantly Ni, with or without the presence of Pd. Analysis of used catalysts showed sintering of crystallites con...
The Energy Information Administration (EIA) prepares quarterly, short-term energy supply, demand, and price projections for publication in February, May, August, and November in the Short-Term Energy Outlook (Outlook). An annual supplement analyzes the performance of previous forecasts, compares recent cases with those of other forecasting services, and discusses current topics related to the short-term energy markets. (See Short-Term Energy Outlook Annual Supplement, DOE/EIA-0202.) The forecast period for this issue of the Outlook extends from the third quarter of 1993 through the fourth quarter of 1994. Values for the second quarter of 1993, however, are preliminary EIA estimates (for example, some monthly values for petroleum supply and disposition are derived in part from weekly data reported in the Weekly Petroleum Status Report) or are calculated from model simulations using the latest exogenous ...
This is the ninth quarterly report as required by the Hanford Federal Facility Agreement and Consent Order (Ecology et al. 1990), also known as the Tri-Party Agreement, established between the US Department of Energy (DOE), the US Environmental Protection Agency (EPA), and the Washington State Department of Ecology (Ecology). The Tri-Party Agreement sets the plan and schedule for achieving regulatory compliance and cleanup of waste sites at the Hanford Site. This report covers progress for the quarter that ended June 30, 1991. A total of 87 milestones have been completed to date. 39 refs., 1 fig.
This report presents a brief description of the fabrication and advantages of a composite, carbon-metal fiber material which does not require lubrication.
cellulose casing material made by Food Products Division,. Union Carbide Corporation. tion of the anode from oxygen generated at the charging electrode. ...
Radon concentration measurements at 50 locations in the monitoring network at Canonsburg, Pa., are reported for the quarterly period of April 29 to July 28, 1980. In addition, a summary of all data from the date of initiation of the network (covering the period January 29 to July 28, 1980) is presented for comparison purposes. Average background in the Canonsburg area for the quarterly period was 0.21 pCi/liter with a range of 0.16 to 0.26 pCi/liter. This compares with an average for the first quarter of 0.18 pCi/liter and a range of 0.12 to 0.23 pCi/liter. Concentrations ranging from 0.27 to 0.75 pCi/liter at 17 locations exceeded the background range. These locations are predominantly downwind of the site in an easterly direction. A similar pattern is evident from the summary of data for the first two quarters.
The magnetic susceptibility and electrical resistivity in cerium and neodymium titanate bronzes in Ln/sub 2/3+x/TiO/sub 3+y/ of the perovskite structure were investigated in the temperature range 77-450/sup 0/K. The deviation of the 1/x = f(T) dependence from the Curie-Weiss law, found for a majority of the compositions, was interpreted from the crystal-field effect based on the state of the Ce/sup 3 +/ and Nd/sup 3 +/ cations. For a number of the phases, a transition from metallic conductivity at high temperatures to semiconducting conductivity was detected at temperatures below 200-250/sup 0/K, which agrees well with the conclusion about the temperature dependence of x, related to the subsystem of Ti/sup 3 +/ cations.
This work studied the effect of the nature of the metal on the performance of Co/CeO{sub 2}, Pd/CeO{sub 2} and Pt/CeO{sub 2} catalysts in the partial oxidation of ethanol. Infrared spectroscopy of adsorbed ethanol and temperature programmed desorption of ethanol were performed in order to establish the reaction mechanism. Catalytic experiments revealed that the product distribution is strongly affected by the nature of the metal. Acetaldehyde was practically the only product formed on a Co/CeO{sub 2} catalyst while methane was also produced on Pt/CeO{sub 2} and Pd/CeO{sub 2} catalysts. These results were explained through a reaction mechanism proposed by the characterization techniques. Co/CeO{sub 2} and Pt/CeO{sub 2} catalysts show mainly ethoxy species at room temperature whereas acetate species is mainly formed on the Pd/CeO{sub 2} catalyst. The ethoxy species can undergo further ...
A catalytic process for the oxidation of sulfur-containing gases , E.G., sulfur dioxide and simultaneous production of sulfuric acid wherein a sulfur-containing gas is reacted with an oxygencontaining gas in the presence of a catalyst comprising an iron group metal on a solid support comprising a zeolite in a silicaalumina matrix.
The oxidative dehydrogenation (OXDH) of n-butane, 1-butene, and trans-2-butene on different vanadia catalysts has been compared. MgO, alumina, and Mg-Al mixed oxides with Mg/(Al + Mg) ratios of 0.25 and 0.75 were used as supports. The catalytic data indicate that the higher the acid character of catalysts the lower is both the selectivity to C{sub 4}-olefins from n-butane and the selectivity to butadiene from both 1-butene or trans-2-butene. Thus, OXDH reactions are mainly observed from n-butane and butenes on basic catalysts. The different catalytic performance of both types of catalysts is a consequence of the isomerization of olefins on acid sites, which appears to be a competitive reaction with the selective way, i.e., the oxydehydrogenation process by a redox mechanism. Infrared spectroscopy data of 1-butene adsorbed on supported vanadium oxide catalysts suggest the presence of ...
The authors investigate the possibility of the direct heterogeneous catalytic synthesis of ethylbenzoate from benzonitrile. The catalysts tested were oxides of aluminium, titanium, and vanadium. The main conversion product detected chromatographically was ethylbenzoate; benzaldehyde, benzamide, and benzanilide were also identified. Aluminium oxide was found to be the most effective catalyst.
The overall objective of this research work was to prepare hydrocracking catalysts using amorphous silica-alumina (ASA) supports in combination with USY and {beta}-zeolites. Three supports: namely silica-alumina, USY and {beta}-zeolites were selected to prepare the extrudates using AP-1 as a binder, while two metal pairs: namely Ni-W and Ni-Mo were loaded on the extrudates through co-impregnation using incipient wetness technique. The catalysts were then calcined at 550C for 2h. The catalysts were tested in a fixed-bed flow reaction system for their activity, using desulfurized vacuum gas oil (DS-VGO) as a feedstock. The catalytic evaluation results of the catalysts showed that {beta}-zeolite alone and in combination with the ASA used in this study, has a potential as a support for developing heavy oil hydrocracking catalysts. A balance of weak and strong acidities of {beta}-zeolite ...
The abstracts of all the presentations (1 plenary session, 2 keynotes, 52 oral communications, 496 posters) of the thematic session 1: 'catalyst preparation and characterization' are gathered in the CD-Rom of the conference. The main application described concerns the petroleum industry. (O.M.)
A process is claimed for selectively preparing alpha-olefins having from 2 to about 22 carbon atoms by contacting a gaseous mixture containing carbon monoxide and hydrogen with an iron titanate alkali metal hydroxide catalyst at reaction conditions correlated so as to favor the formation of a substantial proportion of such alpha-olefin product.
Pd-Ag bimetallic catalysts, supported on gamma-Al2O3, have been evaluated as exhaust catalysts for methanol-fueled vehicles. Laboratory studies have shown that a 0.01% Pd-5% Ag catalyst has greater CO and CH3OH oxidation activity than either 0.01% Pd or 5% Ag catalysts alone. Moreover, Pd and Ag interact synergistically in the bimetallic catalyst to produce greater CO and CH3OH oxidation rates and lower yields of methanol partial oxidation products than expected from a mixture of the single-component catalysts. The Pd-Ag synergism results from Pd promoting the rate of O2 adsorption and reaction with CO and CH3OH on Ag. Rate enhancement by the bimetallic catalyst is greatest at short reactor residence times where the oxygen adsorption rate limits the overall reaction rate.
Reinforced (heterogel) silicate materials containing an amorphous and a crystalline phase are being used more and more industry. Such systems are energetically unsaturated and therefore promising for use in catalysts. The authors used two reinforced materials as supports: an aluminosilicate containing a zeolite (the cracking catalyst, tseokar) and asbestos-containing aluminosilicate. The active component was introduced by impregnation, and this was followed by heat treatment during which the chemical composition and porous structure were formed. The impregnating mixture consisted of solutions of potassium sulfate and vanadate of the required concentrations. The testing shows that reinforced heterogel systems are promising as support materials for sulfuric acid catalysts.
A method for analyzing the experimental results of coal liquefaction reactions which is applicable to a number of aspects of coal liquefaction research and process control, including rapid selectivity and performance screening for catalysts; correlation of laboratory results with process parameters; and optimization of product yield with plant process conditions is described here. Ternary diagrams of product/by-product distributions for the coal liquefaction using Co/Mo catalysts combined with a hyperbolic relationship for the conversion of various hydrocarbon fractions can be used for catalyst screening. A hydrogen consumption diagram used to provide a more significant selectivity test than the hyperbolic correlation is also included. (BLM)
The increasing environmental concern and promotion of ''green processes'' are forcing the substitution of traditional acid and base homogeneous catalysts by solid ones. Among these heterogeneous catalysts, zeolites and zeotypes can be considered as real ''green'' catalysts, due to their benign nature from an environmental point of view. The importance of these inorganic molecular sieves within the field of heterogeneous catalysis relies not only on their microporous structure and the related shape selectivity, but also on the flexibility of their chemical composition. Modification of the zeolite framework composition results in materials with acidic, basic or redox properties, whereas multifunctional catalysts can be obtained by introducing metals by ion exchange or impregnation procedures...
... analyzer section for angle resolved measurements, and a thin film evaporator with a quartz crystal microbalance to measure the mass deposition. ...
The oxidation of sulfur dioxide in gas diffusion electrodes (GDE) in the presence of a homogeneous catalyst, potassium iodide, is investigated. The influence of this catalyst on the voltage-current (V-I) characteristics of the electrodes and the utilization of sulfur dioxide is determined. It is shown that when using the homogeneous catalyst potassium iodide, the utilization can reach 95-100%.
The catalytic properties of molybdena-alumina catalysts reduced in hydrogen were studied in the function of the reduction temperature, i.e. in the function of the extent of reduction. The deuterium exchange reaction of benzene was used as model catalytic reaction. It was concluded that the reaction rate constant and the multiplicity factor decreased with the extent of reduction parallel with the change in the extent of dehydroxylation of the catalysts. (orig.)
Several kinds of catalysts for coal liquefaction were analysed by means of high pressure differential thermal analysis (DTA). The activity order is as follows: Fe(OH)/sub 3/.Ni(OH)/sub 2/ > 3665 > Fe(OH)/sub 3/.MoO/sub 3/ > Jin Chuan Mineral > concentrated pyrite > Japan red-mud approx. equal to Fe(OH)/sub 3/.CuO approx. equal to no catalyst. If the catalysts are promoted by sulphur., the activity order is 3665 + S > Fe(OH)/sub 3/.Ni(OH)/sub 2/ + S > Fe(OH)O/sub 33/ + S > Japan red mud + S > Fe(OH)O/sub 3/.CuO + S > no catalyst. The kinetic parameters of three catalysts commonly used in the liquefaction of coal were determined.
Platinum and ruthenium in carbon supported Pt and Pt-Ru catalysts were determined by direct and derivative spectrophotometric methods. Complexes of platinum and ruthenium with SnCl(3)(-) ligands (tin(II) chloride in HCl) were used to determine both metals in solutions obtained after digestion of the samples of the catalysts. Platinum in the Pt/C catalyst can be determined in solutions obtained by digestion of the samples in aqua regia. Derivative spectrophotometry was used to determine both metals in the presence of each other in solutions obtained after digestion of samples of the Pt-Ru/C catalyst in the mixture of HCl+HNO(3) (6:1). The first derivative at 377 nm (;zero-crossing' point of ruthenium) and the second-derivative values at 495 nm (;zero-crossing' point of platinum) were used to estimate the concentration of platinum and ruthenium, respectively. PMID:18967441
Rye straw was completely hydroliquefied, using red mud or CoO-MoO{sub 3} as the catalyst. Red mud catalyst exhibited a satisfactory activity only in the presence of sulphur at {approx} 673 K. Depending on reaction conditions, different amounts of gaseous and liquid products were formed. Their product distributions were comparable to those obtained in hydroliquefaction of cellulose and lignin. All results could be described by a model which assumed that: pyrolysis precedes hydrogenation of pyrolysis products; CO and CO{sub 2} are products of pyrolysis reaction; and hydrogen is consumed mainly in hydrodeoxygenation reactions. Therefore, from a practical point of view, red mud, which is known as a coal liquefaction catalyst, can also be recommended as a cheap and powerful catalyst in the hydroliquefaction of biomass. 29 refs., 6 figs., 11 tabs.
Mineral matter in coals is important in various senses for coal liquefaction. It is possible that the catalytic activity is affected by the interaction between catalyst and mineral matter. Iron-based catalyst forms pyrrhotite in the process of liquefaction, but the interaction between it and mineral matter is not known in detail. In this study, the interaction between mineral matter and catalyst and the selective reaction between them were investigated. Tanito Harum coal was used for this study. This coal contains a slight amount of siderite and jarosite besides pyrite as iron compounds. Liquefaction samples were obtained from the 1 t/d NEDOL process PSU. The solid deposits in the reactor mainly contained pyrrhotite and quartz. A slight amount of kaolinite was observed, and pyrite was little remained. It was found that the catalyst (pyrrhotite) often coexisted with quartz, clay and calcite. 8 figs., 2 ...
This report discusses environmental surveillance activities conducted on the Nevada Test Site during the first calendar quarter of 1996. Surveillance activities included collection and analysis of air, noble gas, tritiated water vapor, and other water samples. Samples were analyzed for both radiological and non-radiological effluents.
This report summarizes the Groundwater Monitoring Program conducted by SRS during third quarter 1998. It includes the analytical data, field data, data review, quality control, and other documentation for this program; provides a record of the program's activities; and serves as an official record of the analytical results.
This report summarizes the Groundwater Monitoring Program conducted by the Savannah River site during fourth quarter 1999. It includes the analytical data, field data, data review, quality control, and other documentation for this program; provides a record of the program's activities; and serves as an official records of the analytical results.
Research is presented on oil and gas technologies, advanced systems, soil remediation and remediation of acid mine drainage, applied science research in plastics and petroleum coprocessing, and fossil fuel and hydrocarbon conversion using a hydrogen rich plasmas.
Research is presented on oil and gas technologies, advanced systems for fossil fuels, environmental technologies for remediation and waste management, applied energy science on heavy oil and plastics coprocessing, and fossil fuel and hydrocarbon conversion using hydrogen rich plasma.
Research continued on low severity coal liquefaction. Research using high temperature infrared of cyclic olefins progressed well during this quarter. Several fluorinated solvents were found that provide a high temperature medium for isotetralin and its aromatic and aliphatic analogues.
This quarterly newsletter provides timely news and information about the plans and progress of the Energy Development in Island Nations U.S. Virgin Islands pilot project, including significant events and milestones, work undertaken by each of the five working groups, and EDIN-sponsored renewable energy and energy efficiency projects.
This report summarizes activities of the Amarillo National Resource Center for Plutonium during the quarter. The report describes the Electronic Resource Library; DOE support activities; current and future environmental health and safety programs; pollution prevention and pollution avoidance; communication, education, training, and community involvement programs; and nuclear and other material studies, including plutonium storage and disposition studies.
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The vast majority of fundamental studies of metal oxide selective oxidation catalysts have been performed with single phase systems. These investigations established the basic tenents of the redox mechanism of selective oxidation and ammoxidation catalysis. By comparison, structural and kinetic investigations of multiphase oxide catalysts are less numerous because of the inherent difficulties in understanding the relative contributions of separate phases to the catalytic behavior of the composite catalyst. Some attempts have been made in the past to understand the complex chemistry of multiphase catalysts and additional important insights have been realized more recently. However, a clear understanding of the most significant catalytic interactions between individual phases of a multiphase multicomponent redox catalyst is still lacking. In an effort to provide an understanding and a ...
The oxidative dehydrogenation (ODH) of light alkanes is an alternative way for the production of olefins. A wide variety of catalytic systems has been investigated. Vanadium oxide based catalysts were described in the literature as effective catalysts for the ODH of propane. The catalytic activity and selectivity depend on the kind of support material, the kind of dopants and the formation of complex metal oxide phases. In recent papers it was claimed that both orthovanadate and/or pyrovanadate species are selective for the ODH of propane. Niobia based materials were investigated as catalysts for acidic and selective oxidation type reactions. In the ODH of propane niobia exhibited a high selectivity to propene but the conversion of propane was low. V{sub 2}O{sub 5}-Nb{sub 2}O{sub 5} catalysts proved to be catalytically active and selective and showed no formation of oxygenates. In the present study the ...
The aim of this work is to test the catalytic oxidation of pyridine over zeolite-supported catalysts and to compare the difference in their activities for the oxidation of pyridine. The catalytic oxidation of pyridine pollutant on a series of copper-supported catalysts, inclusive of Cu/beta, Cu/ZSM-5, Cu/MCM-41 and Cu/{gamma}-Al{sub 2}O{sub 3}, in the presence of excess oxygen was studied. The activity of the copper-supported catalysts for the pyridine oxidation could be correlated with the binding energy of oxygen coordinated to metal copper, while the ability to control the yield of NO{sub x} appeared to be strongly dependent on the binding energy of NO bonded to metal copper. On these catalysts, two copper species, Cu(H{sub 2}O){sub 6}{sup 2+} ions and CuO were identified, in which Cu{sup 2+} ions had higher activity for the NO{sub x} control but poorer activity for the pyridine oxidation. Amongst ...
This invention relates with a pot-type catalyst carrier which excels as a catalyst carrier when such heavy oils as ordinary pressure distillation residue, oil sand oil, and shale oil are decomposed or treated by hydrogenation. The conventional pot-type carrier is produced by dropping a small drop of a slurry (containing a catalyst component) onto a particle bed and drying it. But the demerit is a large particle size and less catalyst activity or strength. In this invention, a mixture of such carrier components as allophane, red mud, bauxite and latellite, etc.. 60 - 80 weight parts. and a binder 20 - 40 weight parts is added with water to form a slurry of 10 - 30 weight% solid concentration. Slurry is wet-crushed to make the average particle size 0.6 - 2.0 micron, then spray-dried and burned to obtain a pot-type catalyst carrier with average particle size 30 - 200 micron and ...
Influence of residual K{sup +} on the preferential oxidation of CO in excess hydrogen (PROX) over CuO-CeO{sub 2} catalysts was investigated. CuO-CeO{sub 2} catalysts were characterized by BET, ICP, XRD, UV-Raman and TPR techniques. The results showed that the existence of residual K{sup +} made {alpha} peak in TPR of CuO-CeO{sub 2} catalysts shift to higher temperatures and depressed the PROX in the absence of CO{sub 2} and H{sub 2}O in the feed over CuO-CeO{sub 2} catalysts. However, small amount of residual K{sup +} was beneficial to the catalytic performance of CuO-CeO{sub 2} catalysts in the PROX in the presence of CO{sub 2} and H{sub 2}O in the feed. Consequently, residual K{sup +} with an appropriate content was beneficial to improve the catalytic performance of CuO-CeO{sub 2} catalysts in the presence of CO{sub 2} and H{sub 2}O. (author)
10%Pt/C catalysts were prepared by liquid reduction method. PTFE and Pt/ C catalysts were adhered to porous metal and hydrophobic Pt/C/PTFE catalysts were prepared. The structure and size of Pt crystal particles of Pt/C catalysts were analyzed by XRD, and their mean size was 3.1 nm. The dispersion state of Pt/C and PTFE was analyzed by SEM, and they had good dispersion mostly, but PTFE membrane could be observed on local parts of Pt/C/PTFE surface. Because of low hydrophobicity, Pt/C/ PTFE catalysts have low activity when the mass ratio of PTFE and Pt/C is 0.5: 1, and their catalytic activity increases markedly when the ratio is 1:1. When the ratio increases again, more Pt active sites would be covered by PTFE and interior diffusion effect would increase, which result in the decrease of catalytic activity of Pt/C/PTFE. By PTFE pretreatment of porous metal carrier, the activity of ...
The production of hydrogen from the two-stage pyrolysis-gasification of polypropylene using a Ni/CeO{sub 2}/ZSM-5 catalyst has been investigated. Experiments were conducted on CeO{sub 2} loading, calcination temperature and Ni loading of the Ni/CeO{sub 2}/ZSM-5 catalyst in relation to hydrogen production. The results indicated that with increasing CeO{sub 2} loading from 5 to 30 wt.% for the 10 wt.% Ni/CeO{sub 2}/ZSM-5 catalyst calcined at 750 C, hydrogen concentration in the gas product and the theoretical potential hydrogen production were decreased from 63.0 to 49.8 vol.% and 50.4 to 21.6 wt.%, respectively. In addition, the amount of coke deposited on the catalyst was reduced from 9.5 to 6.2 wt.%. The calcination temperature had little influence on hydrogen production for the catalyst containing 5 wt.% of CeO{sub 2}. However, for the 10 wt.% Ni/CeO{sub 2}/ZSM-5 ...
Performance of various catalysts for hydrogenation of recycle solvent was evaluated for the operation of NEDOL process 1 t/d process supporting unit (PSU). Distillate between 220 and 538{degree}C derived from the liquefaction of Tanito Harum coal was used as recycle solvent. Deactivation behaviors of catalysts were compared using a prediction equation of catalyst life, by which aromatic carbon index (fa) after hydrogenation can be determined from the fa of recycle oil before hydrogenation, reaction temperature, and total hydrogenation time. Total hydrogenation time satisfying the {Delta}fa, 0.05 before and after hydrogenation were 8,000, 4,000, and 2,000 hours for NiMo-based catalysts C, A, and B, respectively. Catalyst C showed the longest life. Used catalysts were also characterized. The catalyst C showed larger mean pore size than those ...
The catalytic nature of Mo(CO)/sub 6/ supported on ..gamma..-Al/sub 2/O/sub 3/, KOH-doped ..gamma..-Al/sub 2/O/sub 3/, and HY-zeolite was investigated in CO oxidation with N/sub 2/O in comparison with that of a conventional partially reduced MoO/sub 3//..gamma..-Al/sub 2/O/sub 3/ catalyst. Kinetic parameters of this reaction were obtained in the range 0 to 100/sup 0/C; the rate law r = kP/sub N/sub 2/O//sup 1/P/sub CO//sup 0/ was found on all catalysts, and the activation energy was estimated to be 9.1 kcal/mol on the Mo(CO)/sub 6/-derived catalysts and 7.1 kcal/mol on the partially reduced MoO/sub 3//..gamma..-Al/sub 2/O/sub 3/ catalyst. Maximum catalytic activities were obtained by activating the Mo(CO)/sub 6/-derived catalysts at 400/sup 0/C. To obtain similar activity on the MoO/sub 3//..gamma..-Al/sub 2/O/sub 3/ catalyst, it was necessary to reduce at ...
During third quarter 1994, samples from AMB groundwater monitoring wells at the Metallurgical Laboratory Hazardous Waste Management Facility (Met Lab HWMF) were analyzed for selected heavy metals, indicator parameters, radionuclides, volatile organic compounds, and other constituents. Eight parameters exceeded standards during the quarter. As in previous quarters, tetrachloroethylene and trichloroethylene exceeded final Primary Drinking Water Standards (PDWS). Bis(2-ethylhexyl) phthalate exceeded final PDWS in one well. Aluminum, iron, manganese, tin, and total organic halogens exceeded the Savannah River Site (SRS) Flag 2 criteria. Groundwater flow direction and rate in the M-Area Aquifer Zone were similar to previous quarters. Conditions affecting determination of groundwater flow directions and rates in the Upper Lost Lake Aquifer Zone, Lower Lost Lake Aquifer Zone, and the Middle Sand Aquifer Zone ...
This quarterly report covers activities of the Two-Stage, Close- Coupled Catalytic Liquefaction of Coal program during the period January 1,--March 31,1992, at Hydrocarbon Research, Inc. in Lawrenceville and Princeton, New Jersey. This DOE contract period is from October 1, 1988 to September 30, 1992. The overall purpose of the program is to achieve higher yields of better quality transportation and turbine fuels and to lower the capital and production costs in order to make the products from direct coal liquefaction competitive with other fossil fuel products. The quarterly report covers work on Laboratory Testing, PDU Activities and Administration.
This report summarizes the 1981 operating and test data obtained at the six ton per day Advanced Coal Liquefaction Research and Development Facility in Wilsonville, Alabama. Special emphasis is placed on data accumulated during the fourth quarter of 1981. The Wilsonville R and D Facility was in operation 71% of 1981 (70% of the fourth quarter) with scheduled shutdowns accounting for 23% of the downtime (28% during the fourth quarter). Kentucky 9 coal from the Fies mine was processed in all runs conducted during 1981 (Runs 222 through 235). The hydrotreater (HTR) unit was brought on stream successfully in May 1981. The three process units of the Wilsonville facility were operated in a non-integrated mode during the second half of 1981. Significant data was obtained and is summarized.
The paper discusses two petrochemical selective oxidation reactions namely the practised formation of styrene (STY) and the desired oxidative functionalisation of propane. The present knowledge about the mode of operation of oxide catalysts is critically considered. The dehydrogenation of ethylbenzene (EB) should be described by an oxidehydration with water acting as oxidant. The potential role of the coke formed during catalytic reaction as co-catalyst will be discussed. Selective oxidation is connected with the participation of lattice oxygen mechanism which transforms unselective gas phase oxygen into selective oxygen. The atomistic description of this process is still quite unclear as well as the electron structural properties of the activated oxygen atom. The Role of solid state acidity as compared to the role of lattice oxygen is much less well investigated modern multiphase-multielement oxide (MMO) catalysts. The ...
Red mud is a waste product of the aluminium refining industry. It is composed of aluminium hydroxide and iron oxide. This study examined the feasibility of using red mud as a catalyst to eliminate volatile organic compounds in atmospheric pollutants. Volatile organic compounds can be eliminated by thermal oxidation between 600 and 1100 degrees C. However, the oxidation of volatile organic compounds can also be accomplished at lower temperatures (200 to 450 degrees C) if a catalyst is present. Currently, the low temperature destruction of volatile organic compounds is not widespread because of the difficulty in deactivating the catalyst. In this study, red mud was calcined in air at 500 degrees C. Under such conditions, the red mud converts to aluminium oxide and iron oxide. These 2 oxides are active and are carbon dioxide selective in the oxidation of volatile organic compounds. The study showed that red mud can be used as ...
Chloromethane, dichloromethane and 1,2-dichloroethane were completely decomposed in air on perovskite-type catalysts (LaMnO{sub 3}, LaCoO{sub 3}, (La{sub 0.84},Sr{sub 0.16})(Mn{sub 0.67},Co{sub 0.33})O{sub 3}) at reaction temperatures above 550C. Besides the main reaction products (carbon dioxide, water and hydrochloric acid), by-products (higher chlorinated-, C-C coupling- and cracking products) were formed in the low temperature range. Depending on the reaction temperature, residence time and kind of chlorinated hydrocarbon a reversible catalyst deactivation takes place. In the case of LaCoO{sub 3} catalysts an irreversible deactivation was observed. X-ray diffraction (XRD) and electron probe microanalysis (EPMA) measurements with the perovskite-type catalysts after interaction of chlorinated hydrocarbons indicate the formation of chlorinated species on the catalyst surface and in ...
Results on the oxidative dehydrogenation of ethane on rare-earth oxide (REO) based catalysts (Na-P-Sm-O, Sm-Sr(Ca)-O, La-Sr-O and Nd-Sr-O) are described. Oxygen adsorption was found to be a key factor which determines the activity of this type of catalysts. Continuous flow experiments in the presence of catalysts which reveal strong oxygen adsorption showed that the reaction mixture is ignited resulting in an enhanced heat generation at the reactor inlet. The heat produced by the oxidative reactions was sufficient under the conditions chosen for the endothermic thermal pyrolysis which takes place preferentially in the gas phase. Ignition of the reaction mixture is an important catalyst function. Contrary to non-catalytic oxidative dehydrogenation, reaction temperatures above 700 C could be achieved without significant external heat input. Ethylene yields of up to 34-45% (S=66-73%) were obtained on ...
The oxidative dehydrodimerization of propylene to C/sub 3/-dimers (1,5-hexadiene and benzene) has been examined at 600/sup 0/C and atmospheric pressure using a (Bi/sub 2/O/sub 3/)/sub 0.85/(La/sub 2/O/sub 3/)/sub 0.15/ oxide ion-conducting catalyst in a reactor where a catalyst disk separates a feed of propylene in helium from air. The surface of the disk exposed to propylene was reoxidized not by gaseous O/sub 2/, but by the dissociative adsorption and reduction of dioxygen at the oxidant side of the disk, followed by oxide ion conduction to replace spent lattice oxygen. Selectivity to C/sub 3/-dimers when using lattice oxide migration to reoxidize the catalyst was considerably greater than when O/sub 2/ was added to the propylene feed under the same reaction conditions. This result supports the proposal that lattice oxygen is predominantly involved in the selective oxidation of propylene to C/sub 3/-dimers, and ...
Proton exchange membrane fuel cells (PEMFCs) are attractive because of their high conversion efficiency, low pollution, lightweight, and high power density. A major area of challenges is the design and engineering of active, robust, and low-cost electrocatalysts. This report discusses recent findings of our investigations of the design and nano-engineering of platinum-vanadium-iron catalysts for use in PEMFC. The membrane electrode assembly was prepared using nano-engineered PtVFe nanoparticles with controlled composition and size supported on carbon as cathode electrocatalysts. The electrocatalytic activity and stability of the catalysts have been characterized by both rotating disk electrode and membrane electrode assembly measurements. The trimetallic catalysts have been shown to exhibit excellent electrocatalytic performance in PEMFC in comparison with commercial platinum catalysts. The results ...
The NiMo sulfide supported on Ketjen Black (KB) was more effective and yielded lighter oil products containing light fractions with their boiling point below 300{degree}C during the two stage liquefaction combining low temperature and high temperature hydrogenation the conventional NiMo/alumina catalyst and FeS2 catalyst. Although the NiMo/alumina yielded increased oil products during the two stage liquefaction, the lighter oil fractions did not increase and the heavier fractions increased mainly. This suggests that the hydrogenation of aromatic rings and successive cleavage of the rings are necessary for producing the light oil, which is derived from the sufficient hydrogenation of aromatic rings using catalysts. For the two stage reaction with NiMo/KB catalyst, it was considered that sufficient hydrogen was directly transferred to coal molecules at the first stage of the low temperature reaction, ...
High-throughput synthesis and screening methods have been developed for the discovery of highly active catalysts for the control of emissions from stationary and mobile sources. Low temperature CO oxidation, CO methanation, NOx abatement and the destruction of Volatile Organic Compounds (VOCs) will be discussed. The discovery libraries for primary screening consisted of both 11x11 and 16x16 catalyst arrays on 3 inch and 4 inch quartz wafers, respectively. Catalysts were prepared by robotic liquid dispensing techniques and screened for catalytic activity in Symyx's Scanning Mass Spectrometer. The screening protocols encompassed mixed metal oxides, perovskites and supported base and noble metals. Active hits were further optimized in focus libraries using shallower compositional gradients. The ScanMS is a fast serial screening tool that uses flat wafer catalyst surfaces, local laser heating, a ...
Special CoMo/Al{sub 2}O{sub 3} catalysts were prepared for testing in coal liquefaction: a conventional CoMo/Al{sub 2}O{sub 3} catalyst, one containing Zn as a second promoter and one having the alumina acidified with fluorine. Their activities were compared with that of red mud. The experiments were conducted in a stirred autoclave with a subbituminous coal and solvent (tetralin, anthracene oil or creosote oil) at 425{degree}C and 17 MPa. The liquefaction products were fractionated into oils, asphaltenes and preasphaltenes with pentane, toluene and THF. The Co(Zn)Mo/Al{sub 2}O{sub 3} catalysts have far higher activities than red mud. Zn and fluorine have beneficial effects on the catalyst activity. Coal tar distillates give higher conversions and oil + gas yields than tetralin when the prepared catalysts are used. 17 refs., 7 tabs.
This semiannual report for the period October 1983-March 1984 summarizes activities in Sandia National Laboratories' continuing program of coal liquefaction research. The primary goals are to: explore novel catalytic concepts and materials for conversion of coal to liquid fuels; determine the effects of process variables on catalyst deactivation; determine the effects of coal structure and solvent properties on low temperature dissolution; study the kinetics and catalysis of hydrogen transfer reactions; develop an understanding of slurry gelling phenomena; and provide a technical assessment of coal liquefaction processes. During this period, work was performed on: the use of pyrene as a chemical probe of catalyst activity; analysis of catalysts from Wilsonville run 242 using ESCA; atmospheric pressure model compound activity testing of regenerated catalysts from Wilsonville run 242; base ...
The purpose of this study is to prevent the deactivation of catalysts recycled in the 0.1 t/d bench scale unit (BSU). Catalysts recovered during reactions in the BSU and after reactions in the 5-liter autoclave were analyzed, to investigate the influences of the reaction condition on the property and activity of catalysts. Were used {gamma}-iron oxyhydroxide ({gamma}-FeOOH), {alpha}-iron oxyhydroxide ({alpha}-FeOOH), and natural pyrite (FeS2) as catalysts. At the S/Fe atomic ration of 1.2 under the BSU reaction condition, troilite was more easily formed from {gamma}-FeOOH compared with pyrite and {alpha}-FeOOH. As the reaction proceeded through the first, second, and third reactors, the crystal size increased, the pyrrhotite content decreased, and the troilite content increased. Deactivation due to the formation of troilite was irreversible. At the S/Fe of 3.0, however, both the formation of troilite ...
Recently there has been considerable interest in the Cu-ZSM-5 catalysts for the selective reduction of NO by light hydrocarbons for the purpose of atmospheric pollution abatement. Isobutane and n-pentane cracking were studied over Cu zeolite catalysts and these results were compared with their HY analogues at low conversions and at temperatures of 673 K and below. Three forms of the catalysts were used: those reduced in CO at 773 K; those reduced with H[sub 2] at 473 K; and those in the oxidic form (following flushing with He at 773 K). In contrast with an earlier publication, very little difference in activity was found between the two reduced forms of the catalysts did not differ significantly from each other nor from the H-form of the zeolite. They are typical of a Bronsted acid catalysis. The oxidic form of the catalyst produced excess H[sub 2] in increasing amounts with time on ...
The batchwise preparation of molecular sieves for methanol conversion shows some inconsistency in catalytic stability. This is a result mainly of the change of SiO/SUB/2/Al/SUB/2O/SUB/3 in ion exchange to an H-type sieve. The dealumination during ion exchange depends upon crystal size and structural factors, which can be characterised by the cyclohexane adsorption of the raw molecular sieve. A high SiO/SUB/2/Al/SUB/2O/SUB/3 H-molecular sieve can be prepared from a molecular sieve of high adsorption capacity, this leading to a catalyst of higher stability. (4 refs.)
A nitrogen oxides decreasing combustion method comprising: mixing a fuel and air with each other; bringing the mixture obtained into contact with a packed catalyst; and adding a fresh supply of the fuel to the stream obtained to form a mixed gas and causing the mixed gas to undergo non-catalytic thermal combustion, characterized in that only a catalytic reaction or combustion occurs at the packed catalyst; the temperature of the packed catalyst is kept lower than the ignition temperature of the mixture; the adiabatic flame temperature which is reached by the non-catalytic thermal combustion of the mixed gas is lower than the temperature at which the nitrogen oxides occur. 39 figs.
Palladium silicide was formed on the sol-gel derived SiO2 supported Pd catalysts prepared by ion-exchange method (Pd/SiO2-SG-ion). However, the catalysts exhibited superior performances than commercial SiO2 supported ones in liquid-phase semihydrogenation of phenylacetylene. It was probably due to an inhibition of a product of styrene, which is adsorbed on the surface of Pd, more strongly on Pd/SiO2-SG in which Pd is electron-deficient as shown by larger binding energy from XPS results.
Catalytic testing of inorganic catalysts was continued with the highly active sulfate-modified zirconia catalyst prepared here. Using isobutanol as the only reactant over this catalyst, it was demonstrated that high conversion and selectivity to isobutene was achieved at 175[degrees]C. In addition, the high selectivity to isobutene, i.e. 79--86 mol%, was maintained at higher space velocities and higher temperatures. A high productivity of 11.35 mol isobutene was achieved at 225[degrees]C. Utilizing a methanol/isobutanol = 2/1 molar ratio reactant mixture over the ZrO[sub 2]/SO[sub 4][sup 2[minus
One-pot multi-component condensation of benzyl, aldehydes, ammonium acetate and primary amines were used for synthesis of 2,4,5-trisubstituted and 1,2,4,5-tetrasubstituted-1H-imidazole derivatives under MW radiation using amberlyst A-15 as a catalysts. This catalyst has several advantages (simple work-up, low cost and reusability).
The present paper is a comparative study of the cerium-containing nickel catalysts supported on x- and y-zeolites. In general, the addition of cerium ions caused an increase in the catalytic activity for CO hydrogenation and shifted the product selectivity to high molecular weight hydrocarbons. The degree of the effect of cerium additive depends on the ratio of cerium to nickel contents, the reduction temperature, and the nature of the supporting materials. Catalyst characterization, including volumetric hydrogen chemisorption, temperature programmed reduction/desorption, x-ray diffraction, surface area measurements, in-situ infrared spectroscopy and x-ray photoelectron spectroscopy, was performed in order to interpret the phenomena due to the effects of cerium additives and the support effect on Ni/zeolite catalysts.
It was demonstrated that R 2?R 4 saturated monohydric alcohols can be synthesized from CO and H2 in the presence of Fe catalysts containing a carbon support of the Sibunit type with granule sizes of 3?5, 1?2, and 0.05?0.1 mm in a fixed-bed reactor at 3 MPa and 240?300?C. It was found that the activity of Fe/Sibunit catalysts and their selectivity for the formation of liquid synthetic products increased with the size of granules and the amount of iron. The catalysts make it possible to obtain fatty alcohols, in which the fraction of R 2?R 4 alcohols is as high as 75%, in yields to 56 g/m3.
Graphical abstract: - Abstract: Low loading platinum-cobalt (Pt-Co) cathode catalyst on a Nafion(Na+)-bonded carbon layer is fabricated by using galvanostatic pulse technique to show the advantage of electrodeposition for high utilization of catalyst in proton exchange membrane fuel cell (PEMFC). We observed that Pt-Co catalysts evenly exist on the surface of carbon electrode and its thickness is about 5.8 ?m, which is four times thinner than conventional Pt/C. Improved single cell power performance of Pt-Co cathode catalysts with a ratio of 3.2:1 compared with Pt/C is clearly presented.
The development of high performance electrode materials is currently one of the main activities in the field of the low temperature fuel cells, fuelled with H{sub 2}/CO or low molecular weight alcohols. A promising way to attain higher catalytic performance is to add a third element to the best binary catalysts actually used as anode and cathode materials. In Part I of this review an overview of the preparation and structural characteristics of Pt-based ternary catalysts was presented. This part of the review deals with the electrochemical properties of these catalysts regarding their CO tolerance and electrocatalytic activity for methanol and ethanol oxidation in the case of anode materials, and their activity for oxygen reduction and stability in fuel cell conditions when used as cathode materials. (author)
The photocatalyzed degradation of pyridine in the gas phase was investigated using titanium dioxide semiconductor supported on mordenite. The complete mineralization was found to occur over a catalyst containing 75 wt% TiO{sub 2} and 25 wt% mordenite in about 180 min in the presence of saturated water vapor at O{degrees}C (4.6 Torr). Low water vapor pressure of 0.096 Torr was found to be sufficient to achieve a reasonably high percentage and rate of degradation. Diffusion of pyridine within the catalyst adversely affects the activity when the thickness of the catalyst coating exceeds the penetration depth of illumination. The activity of the zeolite-supported catalysts was higher than that of TiO{sub 2}. The photonic efficiency for the complete mineralization of pyridine to CO{sub 2} was determined to be 0.48. 29 refs., 6 refs., 1 tab.
The performance of Ag-promoted Pd/Al2O3 catalysts, which were prepared by the selective deposition of Ag onto Pd using a surface redox (SR) method, during acetylene hydrogenation was compared with that of catalysts prepared by impregnation. The Pd surface was more effectively modified with Ag added by SR, even when small amounts of Ag were added. The catalyst prepared by SR showed a higher ethylene selectivity than the one prepared by impregnation, because SR allowed both the preferential deposition of Ag on the low-coordination sites of Pd and a greater electronic modification of Pd by Ag.
A new method of the synthesis of high molecular polybutylene terephthalate (PBT) is developed with the use of Irganox 1010, tris(nonylphenyl) phosphite and hypophosphite as stabilizers and boron nitride or boron oxide as a catalyst is proposed.
As a new composition of matter, alkali metal or ammonium or tetraalkylammonium diazidoperfluorophthalocyanatoferrate. Other embodiments of the invention comprise compositions wherein the metal of the coordination complex is cobalt, manganese and chromium.
Acrylonitrile is a versatile intermediate and is produced by the Sohio ammoxidation process world-wide at a level of 8 billion pounds per year. In the catalytic process, propylene, ammonia and air are converted to acrylonitrile directly. The most widely used catalysts are mixed metal molybdates or antimonates. The current investigation deals with metal tellurates as possible low temperature ammoxidation catalysts. Of the catalysts investigated, iron-selenium-tellurates are of particular interest since they exhibit good ammoxidation activity already at 320/sup 0/C which is about 100/sup 0/C lower than the temperature required for molybdate or antimonate systems. Mechanistically, the tellurates behave more similarly to the antimonates than the molybdates. 3 tabs., 4 figs., 13 refs.
Formaldehyde oxidation was examined in a laboratory reactor over alumina-supported Pt, Pd, Rh, Ag, Cu-Cr, and Pd-Ag catalysts as part of a program to develop catalysts for lean-exhaust methanol-fueled vehicles. In general, the H/sub 2/CO oxidation behavior of the catalysts paralleled the CH/sub 3/OH oxidation behavior reported in Parts 1 and 2 of this series (Appl. Catal. 27(1986) 83; J. Catal. 103(1987) 419). Principal similarities were: high activity of Pt when there was no carbon monoxide (CO) in the feed, but strong inhibition by added CO; lower activity of Ag and Cu-Cr catalysts, but only weak inhibition due to added CO; enhanced activity of the Pd-Ag catalyst compared to Pd and Ag alone for feeds containing CO in addition to H/sub 2/CO; and, relatively poor activity of the Rh catalyst. The most unusual behavior was observed with the Pd ...
Isopropyl chloroacetate has been synthesized by esterification of chloroacetic acid and isopropanol, using lanthanum dodecyl sulfate (LDDS) as the catalyst. Various factors that affected the esterification have been investigated, such as reaction time, different water-carrying agent and the amount of catalyst. Under the condition of 1.2/1 molar ratio of isopropanol to chloroacetic acid, 1.0% catalyst (molar percent of chloroacetic acid), 2.5 h reaction time, 5 mL cyclohexane as water-carrying agent and reflux temperature, the esterification conversion of isopropyl chloroacetate reaches 98.3%. The catalytic activity of LDDS is almost equal to that of a Bronsted acid. LDDS, as one kind of water-tolerant Lewis acid, is an excellent catalyst compared to the traditional Lewis acid. (author)
Proton exchange membrane (PEM) fuel cells are energy sources that have the ... for H2 /02 PEM fuel cells because their catalysts have properties suitable for 0 ...
Alkali metal doped double perovskites containing manganese and at least one of cobalt, iron and nickel are useful in the oxidative coupling of alkane to higher hydrocarbons.
The fixed bed pilot plant, the catalyst testing procedure, and the calculations for conversion and selectivities were previously described in the technical progress report covering the period of 3/16/88 to 6/16/88 for Contract DE-AC22-87PC79812. Conversions and hydrocarbon selectivities were calculated using data from an on-line gas chromatography (GC) analyzer. Alcohol selectivities were calculated using data from an on-line boiling point GC analyzer which analyzed the liquid product. The catalysts were prepared via the steps of impregnation, calcination, and reduction on a special Y-zeolite-derived support. The impregnation step consisted of evaporation of metal salts on to the support from an aqueous solution. For one catalyst (No. 6531-188) the metal salts were evaporated on to the support from a reverse micelle solution containing the metal salts. All the catalysts were calcined for four hours at ...
Platinum(II) complexes have been investigated in the hydration of alkynes. These catalysts offer improved regioselectivity over Hg(II) counterparts. 1 fig., 2 tabs.
Discusses results of investigations into catalytic properties of various minerals during hydrogenation of Kansk-Achinsk brown coal with a view to replacing synthetic compositions based on molybdenum. Describes tests and equipment used in hydrogenation of grade B-2 Borodinsk deposit coal in tetralin (hydrogen donor). Various by-products of metallurgical processes and compounds separated from tailings containing mainly iron and sulfur and other metals were used as catalysts. States that: minerals containing iron compounds in the form of pyrites, hematites and magnetites exhibit catalytic properties when used in the hydrogenation of brown coal; pyritic catalysts enrich liquid products with hydrogen while sulfur and nitrogen content remains the same; the yield of malthenes with pyritic catalysts is no lower than with alumocobaltmolybdenum catalysts. 18 refs.
The mechanism of the IndolPhos-Rh-catalyzed asymmetric hydrogenation of prochiral olefins has been investigated by means of X-ray crystal structure determination, kinetic measurements, high-pressure NMR spectroscopy, and DFT calculations. The mechanistic study indicates that the reaction follows an unsaturate/dihydride mechanism according to Michaelis-Menten kinetics. A large value of KM (KM=5.01+-0.16 M) is obtained, which indicates that the Rh-solvate complex is the catalyst resting state, which has been observed by high-pressure NMR spectroscopy. DFT calculations on the substrate-catalyst complexes, which are undetectable by experimental means, suggest that the major substrate-catalyst complex leads to the product. Such a mechanism is in accordance with previous studies on the mechanism...
It is estimated that approximately a quarter of patients undergoing coronary intervention may have significant post-procedural creatinine (CK)/creatinine kinase myocardial band (CK-MB) elevations and...Full Text Available
Progress is reported on: radon barrier systems for uranium mill tailings; liner evaluation for uranium mill tailings; revegetation/rock cover for stabilization of inactive U-tailings sites; and application of long-term chemical biobarriers for uranium tailings.
This report describes a quality assurance program plan for the Yucca Mountain Project. Aspects of the plan include: document control, equipment maintenance and calibration, process control, audits, computer software, and inspections. (CBS)
UNEP will provide in the first CPR quarterly report of 2011 the financial statements for 2010. ...for assessing and rating programme performance UNEP to work with the CPR to identify better ways of streamlining reporting requirements ...in 2011 to achieve the ratios requested by the CPR dependent on receipt of contributions originally planned for the
Laser-assisted processing techniques for producing high-quality solar cell metallization patterns are being investigated, developed, and characterized. The tasks comprising these investigations are outlined.
The biological accumulation of heavy metals and cesium, strontium, and uranium in plants is discussed. The role of nutrient deficiencies and foliar treatments of manganese and iron compounds is described.
The report presents detailed technical information concerning application of flue gas desulfurization (FGD) systems to industrial boilers. The information was obtained by a survey of plant personnel, control system vendors, regulatory agencies, and consulting engineering firms. T...
DOE is supporting the development of several conversion processes that are currently in the pilot plant stage. Each of these processes is described briefly and information given as to contractor, contract, funding, site and current progress. Several support projects are treated similarly. (LTN)
This report consists of an executive summary; eight sections dealing with various processes for coal liquefaction and research and development engineering services; and a glossary. An abstract was prepared for each of the eight sections. (EJH)
This report describes research performed by the Morgantown Energy Technology Center in the following areas: oil and gas; advanced systems describing a coal solid fuel and an eastern shale oil residue waste program; environmental remediation; and waste management technologies.
Polypeptides, copolymers of #alpha#-amino acids and #alpha#-hydroxy acids, could prove to be a valuable new class of synthetic biodegradable polymers. In this paper. steps in synthesis of poly (dl-lactide-co-3, 6-dimethylmorpholine-2,5-dione) from dl-lactide and dl-3,6-dimethylmorpholine-2,5-dione was explained. dl-Lactide was synthesized from lactic acid. In the reaction of 2-bromopropionyl chloride and dl-alanine, N-(2-bromopropionyl)-dl-alanine was prepared and this material was converted to its salt and finally this salt was converted to 3,6-dimethylmorpholine-2,5-dione in a sublime r. These two monomers, that is d l-lactide and dl-3,6-dimethylmorpholine-2,5-dione was polymerized by ring-opening polymerization. FT-IR, "1H NMR, "1"3C NMR Spectra were used for structure elucidation of all intermediate compounds and final product.
The magnetic susceptibility of Y_2Cu_2O_5, Y_2BaCuO_5, and Y_2Ba_2O_5 single-phase compounds in weak magnetic fields (H_0=0.1--20 Oe) and moderate magnetic fields (H_0#=#0.2 Oe it converts into a paramagnetic maximum #chi#(T) which corresponds to an antiferromagnetic transition. In a moderate magnetic field H=500 Oe a normal Curie-Weiss law, #chi##approx##mu#"2_e_f_f (T-#theta#) is observed. At temperatures T=150--300 K, #theta#=38 K and #mu#_e_f_f#approx#2.2 #mu#_B/at. Cu. At T<150 k the temperature dependence of #chi# is described by a simple Curie law with #theta##approx#0. Although the paramagnetic signal is extremely weak, in the Y_2Ba_2O_5 compound the curve of #chi#(T, H_0=100 Oe) for a Y_2ba_2O_5 sample exhibits a slightly smeared maximum at a temperature T#approx#13 K.
Purpose: To evaluate a T_2-weighted URSE sequence for the assessment of pulmonary infiltrations in comparison to CT. Methods: 28 MRT scans of 22 patients with confirmed pneumonia were recorded on a 1.5 Tesla apparatus with an expiratory and diastolic triggered, T_2-weighted ultrafast-spin-echo sequence in axial slice mode with the following parameters: TR_e_f_f/T_E/Turbofactor 2000-4000/90 ms/21-23; slice thickness/separation 6/0.6 mm; FOV 360 mm; 24 slices. 24 spiral CTs (sice thickness/table advance: 1-2 mm/10 mm) were available for comparison. The separate evaluation of MRTs and CTs was performed by three radiologists in a consensus procedure with regard to pulmonary lesions (e.g., infiltration, round foci, net patterns) and image quality of the MRTs (4-step scale). Results: In 71% of the cases the CTs and MRTs agreed with the diagnosis and representation of the lesions, in 25% MRT was superior. MRT was better for the detection of pulmonary abscesses. In 93% the ...
IntroductionCopper(II)-diacetyl-bis(N4-methylthiosemicarbazone), or Cu-ATSM, a hypoxia imaging agent, has been shown to be predictive of response to traditional cancer therapies in patients with a wide range of tumors. It is known that the environment of the tumor results in a myriad of physiological consequences, including hypoxia, alterations in metabolism and proliferation. In an effort to better characterize the relationships between Cu-ATSM and other prominent radiopharmaceuticals, this current study was undertaken to compare the regional distribution of 64Cu-ATSM with [18F]fluoromisonidazole (18F-FMISO), [18F]fluoro-2-deoxy-d-glucose (18F-FDG) and [18F]fluorothymidine (18F-FLT) in 9L tumors.MethodsTaking advantage of the different half-life of 18F (t1/2=110 min) in comparison to 64Cu...
British Columbia is rich in resources of coal but is deficient in resources of liquid petroleum. The overall objective of the B.C. Research Coal Liquefaction Program is to provide sufficient technical data to identify and evaluate coal conversion opportunities in the province. In this first quarterly report, liquefaction test systems are discussed and results from the testing of equipment, procedures and analytical methods using coal samples from Sukunka (N.E. coal) and Hat Creek (central interior) are presented. The proposed program to be undertaken over the next four years is outlined.
In 2009, the Atmospheric Radiation Measurement (ARM) Program and the Climate Change Prediction Program (CCPP) have been asked to produce joint science metrics. For CCPP, the second quarter metrics are reported in Evaluation of Simulated Precipitation in CCSM3: Annual Cycle Performance Metrics at Watershed Scales. For ARM, the metrics will produce and make available new continuous time series of radiative fluxes based on one year of observations from Barrow, Alaska, during the International Polar Year and report on comparisons of observations with baseline simulations of the Community Climate System Model (CCSM).
The US Department of Energy (DOE) Office of Remedial Action and Waste Technology established the Technical Measurements Center (TMC) at the DOE Grand Junction Projects Office (GJPO) in Grand Junction, Colorado, to standardize, calibrate, and compare measurements made in support of DOE remedial action programs. Outdoor radon concentration measurements were made by the TMC in Shiprock, New Mexico, to compare two different methods of measuring radon in an attempt to determine the feasibility of using passive alpha-track detectors to assess the adequacy of remedial action undertaken at the Shiprock uranium mill tailings pile. The results of the first three quarters of monitoring have been detailed in previous reports. An analysis of the data from the fourth quarter of monitoring at Shiprock reveals a somewhat poorer correlation between the two sets of measurements than was seen in the third quarter of this study, but a better ...
The heterogeneous solid catalyst, mercaptopropylsilica (MPS), has been prepared by a modified procedure in water and its structure confirmed by solid state carbon-13 CP-MAS NMR spectrum. This catalyst has been efficiently utilized for the synthesis of a wide variety of tri-, tetrasubstituted imidazoles and their bis-analogues at room temperature. The protocol was further explored for the synthesis of the drug trifenagrel.
Ni catalysts supported on {gamma}-Al{sub 2}O{sub 3}, CeO{sub 2} and CeO{sub 2}-Al{sub 2}O{sub 3} systems were tested for catalytic CO{sub 2} reforming of methane into synthesis gas. Ni/CeO{sub 2}-Al{sub 2}O{sub 3} catalysts showed much better catalytic performance than either CeO{sub 2}- or {gamma}-Al{sub 2}O{sub 3}-supported Ni catalysts. CeO{sub 2} as a support for Ni catalysts produced a strong metal-support interaction (SMSI), which reduced the catalytic activity and carbon deposition. However, CeO{sub 2} had positive effect on catalytic activity, stability, and carbon suppression when used as a promoter in Ni/{gamma}-Al{sub 2}O{sub 3} catalysts for this reaction. A weight loading of 1-5wt% CeO{sub 2} was found to be the optimum. Ni catalysts with CeO{sub 2} promoters reduced the chemical interaction between nickel and support, resulting in an increase in ...
In order to design catalysts suitable for primary liquefaction stage and secondary upgrading stage respectively in the multi-stage liquefaction process, various carbon-supported catalysts were prepared. Catalytic activities of them were investigated for the hydrogenation of 1-methylnaphthalene, to discuss the influences of metals and carbon species on the catalytic activity. Various water soluble and oil soluble Mo and Ni salts were used for NiMo supported catalysts. Among various carbon supports, Ketjen Black (KB) was effective for preparing the catalyst showing the most excellent hydrogenation activity. The KB and Black Pearl 2000 (BP2000) showing high hydrogenation activity were fine particles having high specific surface area more than 1000 m{sup 2}/g and primary particle diameter around 30 nm. This was inferred to contribute to the high dispersion support of active metals. Since such fine particles ...
Standard SCR catalysts possess high activity for the hydrolysis of HNCO and thus explain the suitability of urea as a selective reducing agent for NO{sub x}. At high space velocities HNCO-slip can get perceptible over the entire temperature range. This can be attributed to the fact that the temperature dependence is strong for the SCR reaction, but weak for the hydrolysis reaction. (author) 3 figs., 5 refs.
This patent describes a catalyst comprising: (a) a non-zeolitic inorganic oxide matrix, and (b) an ultrastable Y-type crystalline zeolite, the ziolite having been pretreated by contacting the zeolite with a phosphorus compound selected from the group consisting of phosphoric acid, phosphorous acid, a salt of phosphoric acid, a salt of phosphorous acid, and mixtures thereof for a time sufficient to composite an effective amount of phosphorus with the zeolite.
On handling nitric solutions in the glove box nitrous gases are formed that are sucked off via a heated activated charcoal filter and a catalyst cartridge containing e.g. the FG 590 H catalist (Degussa). By the activated charcoal the nitrous gases are reduced to N/sub 2/ and CO gas; the catalyst will oxidize CO to CO/sub 2/. The CO/sub 2/ obtained is discharged through an exhaust air filter in the glove box.
Co-processing of Battle River coal and Cold Lake oil sand bitumen from Canada was carried out in the presence of Ni-Mo, Co-Mo and red-mud/sulfur catalysts under reaction conditions of 400-450{degree}C, 10-120 min and 22-23 MPa of reaction hydrogen pressure by using a 500 ml shaking-type autoclave. The conversion of Battle River coal during the reprocessing was 97.1 wt% (daf) at 450{degree}C for 121 min with Ni-Mo catalyst, higher than 95.7 wt% (daf) at 450{degree}C for 120 min with red-mud/sulfur catalyst and anthracite oil. Cold lake oil sand bitumen was excellent solvent to liquefy Battle River coal comparing with anthracite on. In the presence of Ni-Mo catalyst during the coprocessing, the hydrogen consumption was nearly the same as that with red-mud/sulfur catalyst. Ni-Mo catalyst gave higher conversion of Battle River coal in the initial stage of the ...
CeO{sub 2}-TiO{sub 2} catalysts are prepared by coprecipitation method, and the activity and stability in the catalytic wet air oxidation (CWAO) of phenol are investigated in a batch reactor and packed-bed reactor. CeO{sub 2}-TiO{sub 2} mixed oxides show the higher activity than pure CeO{sub 2} and TiO{sub 2}, and CeO{sub 2}-TiO{sub 2} 1/1 catalyst displays the highest activity in the CWAO of phenol. In a batch reactor, COD and TOC removals are about 100% and 77% after 120 min in the CWAO of phenol over CeO{sub 2}-TiO{sub 2} 1/1 catalyst at reaction temperature of 150 {sup o}C, the total pressure of 3 MPa, phenol concentration of 1000 mg/L, and catalyst dosage of 4 g/L. In a packed-bed reactor using CeO{sub 2}-TiO{sub 2} 1/1 particle catalyst, over 91% COD and 80% TOC removals are obtained at the reaction temperature of 140 {sup o}C, the air total pressure of 3.5 MPa, the phenol ...
The author discusses the accelerated aging tests performed using Hondo and Maya as aging resids with a commercial large pore hydrotreating catalyst. The results from these tests were compared with those obtained under a normal full life test. The test resid was a sample of a typical refinery charge and the activities for sulfur and vanadium removal were determined at 720"0F after successive brief periods of exposure to the heavier oils.
Process solvent was hydrogenated in the brown coal liquefaction, to investigate the influence of it on the prethermal treatment and liquefaction. Consequently, it was found that the n-hexane soluble (HS) yield was improved. In this study, capacity of hydrogen transfer from solvent during prethermal treatment and effects of catalyst were investigated. Since prethermal treatment in oil was effective for improving the oil yield in the presence of hydrogen/catalyst or high hydrogen-donor solvent, influence of hydrogen-donor performance of solvent or addition of catalyst on the hydrogenation behavior of coal and the characteristics of products during prethermal treatment were investigated in relation to successive liquefaction results. As a result, it was found that the increase of HS yield was due to the acceleration of conversion of THF-insoluble using high hydrogen-donor solvent and/or by adding catalyst. ...
A study has been made of the reactor blockages occurring in the course of direct hydroliquefaction of Miike coal, Taiheiyo coal and Yallourn coal briquets in a tubular reactor. The liquefaction tests were carried out at 450 C under 24.6 MPa hydrogen pressure, with red mud and sulfur catalyst. From the observed balances for catalyst and coal ash, it was inferred that reactor blockages are due to sedimentation of catalyst and ash. The conditions for catalyst and coal ash run-off were determined after solvent and slurry flow rates had been altered to suit the type of coal being tested. It was found that ash run-off occurred more readily as the difference between the slurry flow velocity and the natural sedimentation velocity of red mud in the coal liquids increased. Even when ash run-off was occurring, however, the ash concentration of the slurry in the reactor was higher than the concentration in the feed ...
This patent describes a process for the preparation of acrylonitrile or methacrylonitrile by the reaction of propylene or isobutylene, molecular oxygen and ammonia at a temperature of about 200/sup 0/ to 600/sup 0/C in the presence of an oxidation catalyst. The improvement consists of using as the oxidation catalyst an antimony-free catalyst having the atomic ratios described by the formula: X/sub a/A/sub b/C/sub c/Fe/sub d/Bi/sub e/Mo/sub 12/O/sub x/ wherein X is Ga, In or mixtures thereof; A is alkali metal; C is Ni, Co or mixture thereof; and wherein a is 0.01 to about 4; b is 0 to about 4; c and d are 0.01 to about 12; e is 0.01 to about 6; and x is a number sufficient to satisfy the valence requirements of the other elements present. In a process for the preparation of acrylonitrile or methacryloniotrile by the reaction of propylene or isobutylene, molecular oxygen and ammonia at a temperature of about 200/sup 0/ to ...
Because hydrogenation of coal to liquid products (oils) is accompanied by distributions of complex by-product mixtures (IOM, preasphaltenes, asphaltenes and gases) which change as a function of reaction variables (time, temperature and pressure) and reactor configuration, the determination of selectivity relationships for coal liquefaction catalysts has been a difficult and time-consuming task involving numerous experiments to adequately describe catalyst performance over a range of conditions. This paper describes a method for analyzing the experimental results of coal liquefaction reactions which may be applied to a number of aspects of coal liquefaction research and process control, including: rapid selectivity and performance screening for catalysts; correlation of laboratory results with process parameters; and optimization of product yield for plant process conditions. Catalyst selectivity and ...
Pd-Si metallic glasses have been utilized as catalysts in the Fischer-Tropsch reaction. The glasses are selective of ethane, whereas the in-situ crystallized glasses select a range of hydrocarbons characteristic of conventional Pd catalysts. This shift in selectivity has been observed in other hydrogenation reactions. Surface crystallization caused by the reaction conditions causes variable selectivity. Crystallization in reaction conditions has been monitored by DSC. During the course of the grant we developed the use of (+)- apopinene (6,6-dimethyl-1R,5R-bicyclo(3.1.1)hept-2-ene) as a molecular probe for determining the number and kinds of active sites on metallic glass catalysts. To accomplish this we conducted many experiments for comparison on other types of catalysts. These were foils, powders, and highly dispersed metals on several different supports. The glassy surfaces appear to be three ...
It is thought that iron-based catalysts for coal liquefaction exercise their catalytic activity by forming pyrrhotite (Fe(1-x)S). However, there are still a lot of unknown problems remained concerning the formation and agglomeration behaviors of pyrrhotite. These make a difficulty for improving the activity of iron-based catalysts. In this study, sulfiding behaviors of {alpha}-iron oxyhydroxide ({alpha}-FeOOH) and {gamma}-iron oxyhydroxide ({gamma}-FeOOH) were investigated to reveal the formation and agglomeration behaviors of pyrrhotite. It was found that pyrrhotite was easily converted from ferric oxyhydroxide catalysts having large specific surface areas at the sulfiding temperature below 250{degree}C, and fine crystallites of pyrrhotite were formed at the initial stage of sulfiding. Crystal growth of pyrrhotite at the sulfiding temperature over 350{degree}C depended on the catalyst forms. It was ...
For developing coal liquefaction processes, it is an important problem to improve the light oil yield with increased oil yield. It was previously reported that distillate mainly containing lighter fraction can be produced with high oil yield by reducing the iron/sulfur catalyst addition in slurry, by recycling gas in the process operation, by utilizing these effects, and by using heavy oil as recycling solvent. In this study, the maximum distillate yield of Victorian brown coal was investigated through continuous liquefaction using a bench scale unit. In addition, operation conditions for obtaining sufficient oil yield were investigated under the reduced catalyst addition into one-third. Consequently, it was confirmed that the maximum content of lighter fraction in distillate product was obtained with reduced catalyst addition by using heavy oil as recycling solvent, by adopting new catalyst, and by ...
Abstract in english Higher olefins are produced as a by product in a number of refinery processes and are one of the potential raw materials to produce propylene. In the present study, FCC model feed compound was considered to explore the olefin cracking features and options to enhance propylene using 30% SAPO-34 zeolite as catalyst in a micro-reactor. The superior selectivity of propylene (73 wt%) and higher total olefin selectivity was obtained over 30% SAPO-34 catalyst than over Y or ZSM- (more) 5 zeolite catalysts. The thermodynamical constraints were found to be relatively less serious in the case of 1-hexene conversion. Most of the 1-hexene follows a direct cracking pathway to give two propylene molecules, due to weak acid sites and better diffusion opportunities. The higher temperature and short residence time could also suppress the hydrogen transfer reactions. From OPE (olefins performance envelop) the products ...
Palladium/magnetite nanoparticulate catalysts were developed for efficient elimination of halogenated organic pollutants from contaminated wastewater. Particle recovery from treated water can be ensured via magnetic separation. However, in worst-case scenarios, this catalyst removal step might fail, leading to particle release into the environment. Therefore, a toxicological study was conducted to investigate the impact of both pure magnetite and palladium/magnetite nanoparticle exposure upon human skin (HaCaT) and human colon (CaCo-2) cell lines and a cell line from rainbow trout gills (RTgill-W1). To quantify cell viability after particle exposure, three endpoints were examined for all tested cell lines. Additionally, the formation of reactive oxygen species was studied for the human cells. The results showed only minor effects of the particles on the tested cell systems and support the assumption that palladium/magnetite ...
A patent is claimed for a direct coal liquefication process which is carried out by interaction with a paste, consisting of small-fragment coal, oil and catalysts, with H/sub 2/ at increased temperatures and pressures. The catalyst is a mixture of 1 part per weight of Fe-ore that's been activated by aqueous treatment, and 0.1-1.0 powder-form S. The Fe-ore can be magnetite, limonite, hematite, pyrite, ferrous sand or ''red mud'' (byproduct of the Bayer process), with the ''red mud'' and limonite, having a particle size of about 100 mesh is preferable. Activation of Fe-ore includes aqueous treatment in boiling water for 30-120 min with subsequent drying; annealing at a temp. of 300-700/sup 0/C for 10-120 min; submerging into cold water and final drying. The catalyst is added to the paste in the amount of 0.03-0.3 parts per weight to one part of ...
This report presents the results of Run 261 performed at the Advanced Coal Liquefaction R & D Facility in Wilsonville, Alabama. The run started on January 12, 1991 and continued until May 31, 1991, operating in the Close-Coupled Integrated Two-Stage Liquefaction mode processing Illinois No. 6 seam bituminous coal (from Burning star No. 2 mine). In the first part of Run 261, a new bimodal catalyst, EXP-AO-60, was tested for its performance and attrition characteristics in the catalytic/catalytic mode of the CC-ITSL process. The main objective of this part of the run was to obtain good process performance in the low/high temperature mode of operation along with well-defined distillation product end boiling points. In the second part of Run 261, Criterion (Shell) 324 catalyst was tested. The objective of this test was to evaluate the operational stability and catalyst and process performance while processing the high ash ...
Sulfur poisoning from engine fuel and lube is one of the most recognizable degradation mechanisms of a NOx adsorber catalyst system for diesel emission reduction. Even with the availability of 15 ppm sulfur diesel fuel, NOx adsorber will be deactivated without an effective sulfur management. Two general pathways are currently being explored for sulfur management: (1) the use of a disposable SOx trap that can be replaced or rejuvenated offline periodically, and (2) the use of diesel fuel injection in the exhaust and high temperature de-sulfation approach to remove the sulfur poisons to recover the NOx trapping efficiency. The major concern of the de-sulfation process is the many prolonged high temperature rich cycles that catalyst will encounter during its useful life. It is shown that NOx adsorber catalyst suffers some loss of its trapping capacity upon high temperature lean-rich exposure. With the use of a disposable SOx ...
Alkaline promoted active carbon supported iron catalysts are very active in the oxidative dehydrogenation of ethylbenzene to styrene in the presence of carbon dioxide. The best results were obtained at 550 C for a Li-promoted catalyst with a conversion of ethylbenzene of 75% and a selectivity towards styrene of nearly 95%. These results are better than those obtained with industrial catalysts which perform the dehydrogenation process with an excess of water. The main product of the dehydrogenation reaction with CO{sub 2} was styrene, but the following by-products were detected - benzene and toluene. The selectivity towards toluene was always higher than towards benzene. We observed also the formation of carbon monoxide and water, which were produced with a constant molar ratio of about 0.8. The weight of the catalysts increased up to 20% during the reaction due to deposition of carbon. Using a too large ...
The effect of thermal pretreatment in N[sub 2] up to 723 K and the activation treatments in H[sub 2] and an inert atmosphere on the properties of Ni and Co activated-charcoal-supported catalysts were studied. Catalysts were characterized by means of N[sub 2] adsorption at 77 K, H[sub 2] chemisorption at room temperature, thermogravimetric analysis (TGA), X-ray diffraction (XRD), and transmission electron microscopy (TEM). The catalysts' activity and selectivity for acetone hydrogenation to 2-propanol under unusual and severe conditions (473 K and high overall acetone conversion) were also measured. TGA and XRD evidence was found for the charcoal-support-promoted NiO and CoO reduction to the metallic states when the catalysts were subjected to an inert atmosphere above 723 K caused a loss of acetone hydrogenation activity (calculated on a metal load basis) for both the Ni and Co ...
Ceria (CeO{sub 2})-modified PtRu/C catalysts with different compositions of Ru and CeO{sub 2}, viz. PtRu{sub 0.9}(CeO{sub 2}){sub 0.1}/C, PtRu{sub 0.7}(CeO{sub 2}){sub 0.3}/C and PtRu{sub 0.5}(CeO{sub 2}){sub 0.5}/C and unmodified PtRu/C catalyst were synthesized by the sodium borohydride reduction method. Transmission electron microscopic results indicated that the lower concentrated CeO{sub 2}-modified PtRu/C catalysts had almost a similar morphological structure (well-dispersed particles with size around 2.3-2.5nm) with that of the unmodified PtRu/C catalyst. X-ray diffraction and X-ray photoelectron spectroscopy analyses indicated the formation of PtRu alloy and presence of CeO{sub 2} in an amorphous form with a mixed oxidation states (Ce{sup 3+}-Ce{sup 4+}). Electro-catalytic activity of these catalysts for methanol oxidation was investigated by linear sweep voltammetry and ...
Selective catalytic reduction (SCR) of nitrogen oxides(NO{sub x}) in flue gas or engine exhaust gas with hydrocarbons as the reductant has great potential for less expense, less pollution, and easier operation than SCR with ammonia. Methane is the preferred reducing gas because of its low cost and low toxicity. Stable, low-cost catalysts for SCR with methane are required to demonstrate this technology for controlling NO{sub x} emissions. Several cobalt and nickel catalysts on synthetic clay and uranium oxide supports were investigated for their activities in reducing NO{sub x} with methane in the presence of air. The efficiency of the synthetic clay-supported nickel and cobalt catalysts for nitric oxide (NO) reduction with methane as the reducing gas was poor. The nickel oxide-uranium oxide catalyst, which was chosen for its high stability, was also ineffective. Results from the two-step experiments ...
In pre-experiments a tubular reactor was checked whether it is suitable for kinetic measurement on the system of the silver-catalysed partial oxidation of methanol to formaldehyde. Detrimental effects of heat-transfer and mass-transfer on the experimental results were ruled out. Investigations on the characteristics of the reaction showed that it is possible to manipulate the composition of the product mixture by changing the inlet concentration of the reactants. A modified power-law model was established to describe the reaction kinetics. It considers the preadsorption step of oxygen on the catalysts surface and fits the experimental data quite well. During the rapid oxidation the catalysts surface undergoes a drastic change. It gets coarse and has an adsorption capacity of 11 m{sup 2}/g after being exposed to the reaction mixture. (orig.)
This work describes a three-step pre-treatment route for processing spent commercial Ni Mo/Al_2O_3 catalysts. Extraction of soluble coke with n-hexane and/or leaching of foulant elements with oxalic acid were performed before burning insoluble coke under air. Oxidized catalysts were leached with 9 mol L"-"1 sulfuric acid. Iron was the only foulant element partially leached by oxalic acid. The amount of insoluble matter in sulfuric acid was drastically reduced when iron and/or soluble coke were previously removed. Losses of active phase metals (Ni, Mo) during leaching with oxalic acid were compensated by the increase of their recovery in the sulfuric acid leachate. (author)
Porcine pancreatic lipase immobilized on celite particles has been employed as a catalyst for the esterification of dodecanol and decanoic acid in a predominantly organic system. Solvent influence on the equilibrium position and on the catalyst activity has been studied using 20 solvents, including aliphatic and aromatic hydrocarbons, ethers, ketones, nitro- and halogenated hydrocarbons, and esters. The equilibrium constant for esterification correlates well with the solubility of water in the organic solvent, which in turn shows a good relationship with a function of Guttman's donor number and the electron pair acceptance index number of the solvent. This may be rationalized in terms of the requirements for solvation of water and of the reactants. The catalyst activity, measured as the initial rate of the esterification reaction, is best correlated as a function of both n-octanol-water partition coefficient (log P) and ...
Abstract in english Ru(1%)/SiO2 and Cu(1%)Ru(1%)/SiO2 catalysts were prepared by cogelation. The effect of pH and the amount of water on the physical-chemical properties and the catalytic properties of them were analyzed. The acid medium increased the formation of microporosity and the formation of small size of metallic ruthenium particle. The variation of the water quantity used in the gelation not modify considerably the texture neither the dispersion of the noble metal. The reduction lev (more) el of all prepared catalyst was similar, showing displacement in some of reduction peaks. The toluene hydrogenation indicated that the conversion and the quantity of hydrogenate product varied with the pH and the quantity of water used in the gelation. The addition of copper to Ru/SiO2 catalysts diminished the reactive conversion and their hydrogenant activity
In the course of designing a catalytic porous membrane reactor for experimental studies, both inside and outside of the non-reaction zones as well as the two ends of the membrane need to be completely sealed to ensure that there is no flow across the membrane in the non-reaction zone. Experiments show that up to 50% of the total flow across the membrane may be contributed by the axial flow along the wall of the non-reaction zones if only one side of the membrane is sealed. Another problem that cannot be solved by sealing is the capillary flow of the catalyst along the tube wall into the non-reaction zones when the catalyst is doped on the membrane. One of the best ways to avoid this axial flow of catalyst would be to use non-porous tubes in the non-reaction zones and join them with the porous membrane tube. In doing so, the cost of the membrane reactor could be reduced simply because shorter membrane tube is needed.
A dense Pd-Ag membrane reactor (MR) with 100% hydrogen selectivity packed with either Rh/La2O3 or Rh/La2O3-SiO2 as catalysts was used to carry out the dry reforming of methane. The membrane reactor simulation was performed using a well-known reactor model. For this purpose, we employed the equations derived from complete kinetic studies of the dry reforming of methane reaction in connection with both catalysts. In addition, we developed the kinetic equation for the reverse water gas shift reaction (RWGS). The combination of detailed kinetic studies with the measured permeation flux for the Pd-Ag membrane allowed a complete comparison between experimental and simulated operation variables. The variables studied for both catalysts were methane conversion and hydrogen permeation as a function...
Atmospheric pressure tests were performed in which a palladium catalyst ignites and stabilizes the homogeneous combustion of methane. Palladium exhibited a reversible deactivation at temperatures above 750 C, which acted to ``self-regulate`` its operating temperature. A properly treated palladium catalyst could be employed to preheat a methane/air mixture to temperatures required for ignition of gaseous combustion (ca. 800 C) without itself being exposed to the mixture adiabatic flame temperature. The operating temperature of the palladium was found to be relatively insensitive to the methane fuel concentration or catalyst inlet temperature over a wide range of conditions. Thus, palladium is well suited for application in the ignition and stabilization of methane combustion.
A kinetic model based on the Mars-van Krevelen mechanism that allows to describe the microkinetics of the heterogeneously catalysed partial oxidation of {alpha}, {beta}-unsaturated aldehydes is presented. This conversion is represented by a network, composed of the oxidation of the {alpha}, {beta}-unsaturated aldehyde towards the {alpha}, {beta}-unsaturated carboxylic acid and the consecutive oxidation of the acid as well as the parallel reaction of the aldehyde to products of deeper oxidation. The reaction steps of aldehyde respectively acid oxidation and catalyst reoxidation have been investigated separately in transient experiments. The combination of steady state and transient experiments has led to an improved understanding of the interaction of the catalyst with the aldehyde and the carboxylic acids as well as to a support of the kinetic model assumptions. (orig.)
In Polymer Electrolyte Fuel Cell (PEFC) technology the reducing of volume and mass of the fuel cell stack and the improvement of catalyst utilization are of great interest. These parameters affect applicability and system cost. In this work we present an alternative way for reducing the stack volume by combining gas distribution and catalytic active area in one plate. Micro machined glassy carbon electrodes serve as support material for the platinum catalyst, as well as gas distributor at the same time. A comparison of these electrodes with conventional platinum-black gas diffusion electrodes under fuel cell conditions shows that the new system is a promising electrode type for enhanced power density and catalyst utilization. (author) 3 figs., 5 refs.
Hydrogenation of napthalene to tetralin using activated red mud as catalyst was studied as a typical hydrogen-donor system. Under the chosen reaction conditions, unprocessed red mud resulted in a conversion of napthalene of 3.55%. The most active catalyst, prepared by adding 20 wt% of TiO/SUB/2 to the red mud, followed by acid digestion and re-precipitation, resulted in a 58% conversion of naphthalene. This technology may have an important bearing on processes such as coal hydrogenation or crude-oil-residue processing, where the rate of reaction and product quality may depend upon the rate at which a hydrogen-donor solvent can be re-hydrogenated. (7 refs.)
Asphaltenes precipitated from an Arabian Mix vacuum residue were hydrocracked in a batch autoclave at 435 and 460{degree}C for 5-90 min. Experiments without catalyst, with modified red mud and with an industrial Co Mo/Al{sub 2}O{sub 3} catalyst were compared. The products were fractionated into gas, naphtha, oil, asphaltenes and coke. Feed asphaltenes and several product fractions were characterised by elemental analysis, by average molecular mass and by {sup 1}H n.m.r. Due to the hydrogenation activity, both catalysts caused - with similar efficiency - the decrease of coke formation and the increase of quantity and quality of oil. 21 refs., 9 figs., 5 tabs.
Abstract Dynamic testing of a phosphoric acid-based high temperature PEM fuel cell shows a peculiar phenomenon. A certain current loss is observed after temperature cycling at constant voltage. This loss is incidentally recovered by applying a cell voltage spike to open circuit voltage. Experimental investigations into temperature, cell voltage, and ageing effects show that this phenomenon might occur due to the orientation of the adsorbed phosphate species on the platinum catalyst surface. Along with some supporting literature and experimental results, a hypothesis is presented in order to explain this occurrence. Phosphoric acid adsorption hysteresis on platinum catalyst due to temperature cycling could cause the temporary cell current loss. Electrode potential-dependent molecule symmetr...
The structure and catalytic properties of 2 wt.-% Pd/SiO/sub 2/ catalysts promoted with 2 wt.-% MgO and 0.2-5 wt.-% iron have been investigated. Catalysts were characterized by TPR, hydrogen chemisorption, and Moessbauer spectroscopy and their catalytic performance in methanol formation was also measured. At 16 at.-% iron a sharp maximum was observed in the activity which can be interpreted as being due to simultaneous promotion with iron and MgO. Independent mechanisms of promotion were found for the two modifiers: iron influenced the metallic component by forming bimetallic PdFe particles while MgO changed the properties of silica in a favourable way. 6 figs., 29 refs., 1 tab.
A residue in the production of alumina by the Bayer process is red mud. It contains oxides of Fe and Ti, active as hydrogenation catalyst in sulfided form, and whose catalytic activity can be improved by the activation method proposed by Pratt and Christoverson. The paper describes how the development of its activity and selectivity with reaction time was studied for the hydrogenation of a light fraction of an anthracene oil, and compared with untreated sulfided red mud. Catalyst samples were collected at different reaction times, and their texture, morphology and composition characterized by nitrogen adsorption, SEM and SEM-EDX. The loss of catalytic activity of activated sulfided red mud is slower than for untreated sulfided red mud. The main cause of this decrease in catalytic activity is the loss of surface area and superficial Fe.
A Selective Catalytic Reduction (SCR) catalyst was prepared by slurry coating ZSM-5 zeolite onto a cordierite monolith, then subliming an iron salt onto the zeolite, calcining the monolith, and then dipping the monolith either into an aqueous solution of manganese nitrate and cerium nitrate and then calcining, or by similar treatment with separate solutions of manganese nitrate and cerium nitrate. The supported catalyst containing iron, manganese, and cerium showed 80 percent conversion at 113 degrees Celsius of a feed gas containing nitrogen oxides having 4 parts NO to one part NO.sub.2, about one equivalent ammonia, and excess oxygen; conversion improved to 94 percent at 147 degrees Celsius. N.sub.2O was not detected (detection limit: 0.6 percent N.sub.2O).
A Selective Catalytic Reduction (SCR) catalyst was prepared by slurry coating ZSM-5 zeolite onto a cordierite monolith, then subliming an iron salt onto the zeolite, calcining the monolith, and then dipping the monolith either into an aqueous solution of manganese nitrate and cerium nitrate and then calcining, or by similar treatment with separate solutions of manganese nitrate and cerium nitrate. The supported catalyst containing iron, manganese, and cerium showed 80 percent conversion at 113 degrees Celsius of a feed gas containing nitrogen oxides having 4 parts NO to one part NO.sub.2, about one equivalent ammonia, and excess oxygen; conversion improved to 94 percent at 147 degrees Celsius. N.sub.2O was not detected (detection limit: 0.6 percent N.sub.2O).
Red mud has been activated by dissolution in hydrochloric acid and reprecipitation with ammonia. The activated material has been evaluated as a catalyst for the hydrogenation of naphthalene, phenanthrene and pyrene and in the hydroliquefaction of both a high and low rank coal utilizing solvents of high and low hydrogen donating ability. Activation led to a substantial increase in the ability to hydrogenate the model compounds and a significant increase in oil yield was obtained in the hydroliquefaction of a low rank coal in the presence of a poor donor solvent. However, activation did not lead to significant increases in overall yields of liquids in other cases and the activated red mud was significantly less active than a commercial nickel-molybdenum-sulphur catalyst. 27 refs., 1 fig., 5 tabs.
A new heterogeneous catalyst for the esterification of free fatty acids and the transesterification of vegetable oils is reported. The layered compound zinc hydroxide nitrate (Zn5(OH)8(NO3)22H2O) was very effective in the alcoholysis of palm oil and the esterification of lauric acid with m(ethanol), even when hydrated ethanol was used. Over the range of 100-140degreeC, the ester yield was the highest at 140degreeC, while the catalyst concentration had a much greater effect on ester yields than the molar ratio of alcohol to acid did. Total ester contents above 95wt% were obtained in both reactions and 93.2wt% glycerin streams were recovered as a result of methanolysis.
During second quarter 1992, tritium, trichloroethylene, tetrachloroethylene, chloroethene, antimony, 1,1-dichloroethylene, lead, nonvolatile beta, radium-228, thorium-228, or total alpha-emitting radium (radium-226 and radium-228) exceeded the US Environmental Protection Agency Primary Drinking Water Standards (PDWS) in groundwater samples from monitoring wells at the Mixed Waste Management Facility (MWMF) and adjacent facilities. Tritium and trichloroethylene were the most widespread constituents; 55 (48%) of the 115 monitored wells contained elevated tritium activities, and 23 (20%) wells exhibited elevated trichloroethylene concentrations. Sixty-three downgradient wells screened in Aquifer Zone IIB2 (Water Table), Aquifer Zone IIB[sub 2] (Barnwell/McBean), and Aquifer Unit IIA (Congaree) contained concentrations of tritium, trichloroethylene, tetrachloroethylene, chloroethene, antimony, 1,1-dichloroethylene, lead, nonvolatile beta, radium-228, thorium-228, or ...
The aim of this contract is to investigate, develop, and characterize laser-assisted processing techniques utilized to produce the fine-line, thin-metal grid structures that are required to fabricate high-efficiency solar cells. During the first quarter of this contract, a comprehensive literature search was carried out in the various state-of-the-art laser-assisted techniques for metal deposition, including laser chemical vapor deposition and laser photolysis of organometallics, as well as laser-enhanced electroplating. A compact system for the experiments involving laser-assisted photolysis of gas-phase compounds was designed and constructed. The work performed in the second quarter is detailed in this report. Metal deposition experiments have been carried out utilizing laser-assisted pyrolysis of a variety of metal-bearing polymer films and metallo-organic inks spun onto silicon substrates. Laser decomposition of spun-on silver neodecanoate ...
This project is part of PETC`s Advanced Power Systems Program, whose mission is to accelerate the commercialization of affordable, high- efficiency, low emission, coal-fueled electric generating technologies. A process concept - Clear Liquor Scrubbing with Anhydrite Production - was proposed and accepted by PETC as a Phase I project in its Mega-PRDA program. the project integrated three process operations - chloride control upstream of the flue gas desulfurization (FGD) system, a clear liquor process for enhanced SO{sub 2} removal performance, and production of anhydrite (anhydrous calcium sulfate) rather than calcium sulfite or gypsum (calcium sulfate dihydrate). The first step in the project was to perform batch and flow-through experiments in the laboratory to confirm theoretical calculations and preliminary laboratory results concerning anhydrite formation, these laboratory experiments were designed to prove that anhydrite can be produced under conditions that can be reasonably ...
The information reported is for the period October I to December 31, 1993. During this quarter, activities were undertaken in Task 2. Oxygen concentrations were measured in the post-flame region of the entrained flow reactor. The sampling probe was used for the hot gas tests to sample the gas stream. Samples were injected into a gas chromatograph to determine the oxygen concentration. Results agreed with thermoequilibrium calculations that yield equilibrium compositions based on the stoichiometry of the feed gases. The axial temperature distribution along the reactor centerline was measured using a silica-coated platinum-rhodium thermocouple. Two coating techniques were tested and it was found that flame-plating silica to the thermocouple wires produced a thinner coating than a ceramic adhesive technique and therefore a smaller radiation correction. Other activities this quarter included the fabrication of a solids sampling probe support ...
During the first and second quarters of 1994 air samples were collected and analyzed from 54 air particulate/halogen sampling stations, 10 noble gas sampling stations and 19 tritiated water vapor sampling stations. Surface water samples were collected and analyzed from 12 open water supply reservoirs, 8 natural springs, 2 wastewater containment ponds and 9 sewage lagoons. Groundwater samples were obtained brom 10 potable and 1 non-potable supply wells, and 8 drinking water consumption points. Ambient radiation levels were measured at 193 locations.
A phase 2 study has been initiated to investigate surfactant-assisted coal liquefaction, with the objective of quantifying the enhancement in liquid yields and product quality. This report covers the second quarter of work. The major accomplishments were: completion of coal liquefaction autoclave reactor runs with Illinois number 6 coal at processing temperatures of 300, 325, and 350 C, and pressures of 1800 psig; analysis of the filter cake and the filtrate obtained from the treated slurry in each run; and correlation of the coal conversions and the liquid yield quality to the surfactant concentration. An increase in coal conversions and upgrading of the liquid product quality due to surfactant addition was observed for all runs.
A phase 2 study was initiated to investigate surfactant-assisted coal liquefaction, with the objective of quantifying the enhancement in liquid yields and product quality. This publication covers the first quarter of work. The major accomplishments were: the refurbishment of the high-pressure, high-temperature reactor autoclave, the completion of four coal liquefaction runs with Pittsburgh No. 8 coal, two each with and without sodium lignosulfonate surfactant, and the development of an analysis scheme for the product liquid filtrate and filter cake. Initial results at low reactor temperatures show that the addition of the surfactant produces an improvement in conversion yields and an increase in lighter boiling point fractions for the filtrate.
Few major mandates were won or lost in the first quarter of 1993, as the energy industry adopted a conservative approach to its financing needs. However, indications are that energy companies are coming back to the syndicated loan market after this quiet first quarter. Already, Enron, Shell Oil and Coastal have mandated substantial new facilities. Many more companies are expected back in the market over the new few months, including at least one jumbo for a major international name. A number of the industry's top names report that pricing is once again getting more aggressive in response to the high level of liquidity among lenders and a shortage of new mandates over the last few months. (Author)
The OSP (Operating Safety Procedure) required for performance of electrical arc testing of CFC replacement fluids was renewed. Electrical breakdown tests at one atmosphere pressure have been performed for R-22, R-134a, and R-125/R-143a (50:50 blend; R-507), and breakdown products identified. No differences in HCFC breakdown products are seen in the presence or absence of lubricant oils. The design of the high pressure-high temperature test stand has been finalized, and construction initiated during this quarter. Three motor stators and rotors were received from Tecumseh Products Company for use in motor burnout tests. A test plan for the motor breakdown tests is in preparation.
The ORR operated at an average power level of 29.7 MW for 85.3% of the time during this period. The reactor was shut down on fifteen occasions, nine of which were unscheduled. Reactor downtime needed for refueling and checks was normal. The reactor remained available for operation 88.3% of the time. Special tests completed during the quarter included: (1) transfer of LEU fuel elements CLE-202 and NLE-201 from core positions B-9 and B-2 to core positions C-5 and C-6 for continued operation; and (2) calculation of maximum heat flux in LEU elements CLE-201 and NLE-202 in core positions A-2 and A-8. In-service inspections included inspections of ORR decay tank, primary heat exchanger No. 4, and the 24-in. strainer.
The three tasks were completed during this reporting period. During this quarter, work focused on a local structural analysis of the Table Rock field, greater Green River basin (GGRB) in southwestern Wyoming. The ultimate objective of the local analysis is to apply the techniques developed and demonstrated during earlier phases of the project in the Rulison Field area of the Piceance basin for sweet-spot delineation. The primary goal of this work is to focus in on the Table Rock field area in the northern Washakie basin of the Greater Green River basin in support of Union Pacific Resources and DOE planned horizontal drilling efforts. The work plan for the quarter of April 1, 1998--June 30, 1998 consisted of three tasks: (1) Acquire necessary seismic data and depth-convert, (2) Map major fault geometry and analyze displacement vectors, (3) Develop and initiate a natural fracture prediction study.
During this quarter, work began on the regional structural and geologic analysis of the greater Green River basin (GGRB) in southwestern Wyoming, northwestern Colorado and northeastern Utah. The ultimate objective of the regional analysis is to apply the techniques developed and demonstrated during earlier phases of the project to sweet-spot delineation in a relatively new and underexplored play: tight gas from continuous-type Upper Cretaceous reservoirs of the GGRB. The primary goal of this work is to partition and high-grade the greater Green River basin for exploration efforts in the Cretaceous tight gas play. The work plan for the quarter of January 1, 1998--March 31, 1998 consisted of three tasks: (1) Acquire necessary data and develop base map of study area; (2) Process data for analysis; and (3) Initiate structural study. The first task and second tasks were completed during this reporting period. The third task was initiated and work ...
The goal of the work this quarter has been to partition and high-grade the Greater Green River basin for exploration efforts in the Upper Cretaceous tight gas play and to initiate resource assessment of the basin. The work plan for the quarter of July 1-September 30, 1998 comprised three tasks: (1) Refining the exploration process for deep, naturally fractured gas reservoirs; (2) Partitioning of the basin based on structure and areas of overpressure; (3) Examination of the Kinney and Canyon Creek fields with respect to the Cretaceous tight gas play and initiation of the resource assessment of the Vermilion sub-basin partition (which contains these two fields); and (4) Initiation analysis of the Deep Green River Partition with respect to the Stratos well and assessment of the resource in the partition.
Two constructions due to Dr\\'apal produce a group by modifying exactly one quarter of the Cayley table of another group. We present these constructions in a compact way, and generalize them to Moufang loops, using loop extensions. Both constructions preserve associators, the associator subloop, and the nucleus. We conjecture that two Moufang 2-loops of finite order $n$ with equivalent associator can be connected by a series of constructions similar to ours, and offer empirical evidence that this is so for $n=16$, 24, 32; the only interesting cases with $n\\le 32$. We further investigate the way the constructions affect code loops and loops of type $M(G, 2)$. The paper closes with several conjectures and research questions concerning the distance of Moufang loops, classification of small Moufang loops, and generalizations of the two constructions.
Work on the coke oven gas cleaning demonstration project (CCT-11) this quarter has focused on Phase IIB tasks, and include engineering, construction, and training. Additionally, plans for changes in the operating schedule of the coke plant that affect the demonstration project are described. The project Milestone Schedule and Log is shown. Planned Baseline Supplemental Monitoring activities described in the Environmental Monitoring Plan were completed. Testing of the mechanical systems began in June, 1991. The cold commissioning date has been moved back from October 1, 1991 to November 1, 1991 to allow float for miscellaneous finish-up items beyond the electrical contractor`s projected completion date of October 31, 1991.
The purpose of this project is to demonstrate targeted infill and extension drilling opportunities, better determinations of oil-in- place, methods for improved completion efficiency and the suitability of waterflooding in certain shallow-shelf carbonate reservoirs in the Williston Basin, Montana, North Dakota and South Dakota. Improved reservoir characterization utilizing 3-dimensional (3D) and multi-component seismic are being investigated for identification of structural and stratigraphic reservoir compartments. Field demonstrations are in progress to collect data for evaluation of horizontal completions in both the Red River and Ratcliffe. A vertical well in the Red River will test attribute analysis of 3D seismic data for prediction of porosity development. Additional seismic acquisitions and interpretation are in progress for both the Ratcliffe and Red River. A water-injectivity test in a new horizontal completion in the Red Rive B zone at Buffalo Field is scheduled for next ...
Studies continued on organic tracers for use as hydrologic tracers as part of the Yucca Mountain Site Characterization project. This subject report for the quarter 01/01/93 through 03/31/93 discusses the following issues: project organization and responsibilities; quality assurance program; design control; procurement document control; instructions, procedures, and drawings; document control; control of purchased items and services; identification and control of items; control of processes; inspection; test control; control of measuring and test equipment; handling, storage, and shipping; inspection, test, and operating status; control of nonconforming items and conditions; corrective action; quality assurance records; audits; software quality assurance; and scientific investigation.
This report is to present the progress made on the project ''Establishment of an Environmental Control Technology Laboratory (ECTL) with a Circulating Fluidized-Bed Combustion (CFBC) System'' during the period July 1, 2004 through September 30, 2004. The following tasks have been completed. First, renovation of the new Combustion Laboratory and the construction of the Circulating Fluidized-Bed (CFB) Combustor Building have started. Second, the design if the component parts of the CFBC system have been reviewed and finalized so that the drawings may be released to the manufacturers during the next quarter. Third, the experiments for solid waste (chicken litter) incineration have been conducted using a Thermogravimetric Analyzer (TGA). This is in preparation for testing in the simulated fluidized-bed combustor. The experimental results from this study are presented in this report. Finally, the proposed work for the next ...
During this reporting period the experimental apparatus was completed after substantial delays by the manufacturer. The equipment has been fully tested to familiarize the staff with its operating and safety procedures. An initial liquefaction study has begun on samples of Utah coal (60 microns or less) using 50 grams of iron-titanium alloy, 500 ml of tetralin, and 150 grams of powdered coal at 500/sup 0/F and 500 psig. Results will be available in the next quarterly report. A new researcher has been added to the project to address the hydrogen absorption of new and recycled alloy samples. 2 figs.
Correlations between structural aspects of solid materials and their behavior as catalysts are relatively recent. This 20-chapter book focuses on understanding of solid-state mechanisms in heterogeneous catalysis and relationship between catalytic behavior and solid state structure, emphasizing catalysis with oxides, sulfides, and zeolites.
Enzymes are versatile catalysts in laboratories and on an industrial scale; improving their immobilization would be beneficial to broadening their applicability and ensuring their (re)use. Lipid-coated...Full Text Available
A series of silylated Co/SBA-15 catalysts were prepared via the reaction of surface Si-OH of SBA-15 with hexamethyldisilazane (HMDS) under anhydrous, vapor-phase conditions, and then characterized by FT-IR, N2 physisorption, TG, XRD, and TPR-MS. The results showed that organic modification led to a silylated SBA-15 surface composed of stable hydrophobic Si-(CH3)3 species even after calcinations and H2 reduction at 673 K. Furthermore, the hydrophobic surface strongly influenced both metal dispersion and reducibility. Compared with non-silylated Co/SBA, Co/S-SBA (impregnation after silylation) showed a high activity, due to the better cobalt reducibility on the hydrophobic support. However, S-Co/SBA (silylation after impregnation) had the lowest FT activity among all the catalysts, due to the lower cobalt reducibility along with the steric hindrance of grafted -Si(CH3)3 for the re-adsorption of ?-olefins. -- Graphical abstract: The silylation of ...
The effect of neutralizing cations on the secondary reactions of the primary products from CO hydrogenation over ion-exchanged zeolite-supported Ru catalysts was investigated using zeolites with different alkali cations (Li/sup +/, Na/sup +/, K/sup +/, Rb/sup +/, Cs/sup +/). The transformation of olefins (propylene and butene) on the zeolites without the metal, under conditions similar to those used for CO hydrogenation, was also studied in order to understand the effect of the various constituents of the support, i.e., the Broensted acid sites generated during catalyst preparation and the alkali cations, on possible secondary reactions of the primary olefinic products. It was established that secondary acid-catalyzed reactions of these primary products can play a major role in shaping product selectivity during CO hydrogenation over zeolite-supported catalysts. Depending on the concentration and the strength of the acid ...
Propylene polymerizations were carried out with {phi}{sub 2}C(Flu)(Cp)ZrCl{sub 2} and SiMe{sub 2}(Ind)2ZrCl{sub 2} catalysts supported on silica, zeolite sodic mordenite (NaM) and acid mordenite (HM). The polymerizations were performed at different temperatures and varying aluminium/zirconium molar ratios ([Al]/[Zr]). The effect of these reaction parameters on the catalyst activity was investigated using a proposed statistical experimental planning. In the case of f{sub 2}C(Flu)(Cp)ZrCl{sub 2}, SiO{sub 2} and NaM were used as support and the catalyst performance evaluated using toluene and pentane as polymerization solvent. The molecular weight, molecular weight distribution, melting point and crystallinity of the polymers were examined. The results indicate very high activities for the syndiospecific heterogeneous system. Also, the polymers obtained had superior Mw and stereo regularity. (author)
Propylene polymerizations were carried out with #phi#_2C(Flu)(Cp)ZrCl_2 and SiMe_2(Ind)2ZrCl_2 catalysts supported on silica, zeolite sodic mordenite (NaM) and acid mordenite (HM). The polymerizations were performed at different temperatures and varying aluminium/zirconium molar ratios ([Al]/[Zr]). The effect of these reaction parameters on the catalyst activity was investigated using a proposed statistical experimental planning. In the case of f_2C(Flu)(Cp)ZrCl_2, SiO_2 and NaM were used as support and the catalyst performance evaluated using toluene and pentane as polymerization solvent. The molecular weight, molecular weight distribution, melting point and crystallinity of the polymers were examined. The results indicate very high activities for the syndiospecific heterogeneous system. Also, the polymers obtained had superior Mw and stereo regularity. (author)
A laboratory-scale well-mixed thermostatic reactor with continuously blasting air was used to investigate the oxidation inhibition of sulfite in dual alkali flue gas desulfurization (FGD) system. The effects of operating parameters such as pH value and catalyst concentration on the oxidation were studied. Sodium thiosulfate was used in the system, and was found that it significantly inhabited the sulfite oxidation. In the absence of catalyst, sodium thiosulfate at 12.67 mmol/L had an inhibition efficiency of approximately 98%. While in the presence of catalyst, sodium thiosulfate at 26.72 mmol/L had an inhibition efficiency less than 85.0%. The oxidation reaction order of sulfite in the sodium thiosulfate was determined to be -1.90 and -0.55 in the absence and presence of the catalyst, respectively. Apparent activation energy of oxidation inhibition was calculated to be 53.9 kJ/mol. Pilot tests showed ...
The catalytic effects of copper-aluminium-magnesium oxides in the oxidative coupling of phenylethyne is described. The importance of surface properties as a redox site are discussed.
...wood smoke, emissions, pollution, heaters, environment, Earthbeat - 25/5/2002: Woodsmoke, Health & the Environment Love that Planet All in the Mind The Buzz Health Report In Conversation Ockhams Razor Science Show The Lab Health Matters Catalyst Quantum ...
Research programs on coal liquefaction are presented. Major topics include: coprocessing, two-stage liquefaction, low severity liquefaction, coal/catalyst and liquefaction chemistry. Individual projects are processed separately for the data bases. (CBS)
Work continued on the correlations of catalytic activity of metals and surface structure. Work is described in the following areas: CO oxidation on a Cu/Rh(100) Bimetallic catalysts; electronic properties of bimetallic surfaces; and reflection absorption spectroscopy of bimetallic surfaces. 5 figs. (CBS)
This thesis is in the field of gas emission control from automobile and stationary sources. Out of the possible approaches to the elimination of pollutant gases, such as nitrogen oxides (NO{sub x}), one consists in the selective catalytic reduction (SCR) of these NO{sub x} on a suitable heterogeneous catalyst. Ammonia or hydrocarbons are employed as reducing agents. The most important catalysts active in the SCR of NO{sub x} are based on ions of transition metal either supported on several oxides or dispersed in zeolites. The catalysts have been characterized by electron magnetic resonance techniques (EPR, ENDOR, ESEEM) and the interaction of catalysts with nitrogen oxides, with reducing and poisoned agents have been followed with the same techniques. Copper dispersed on alumina and its interaction with both NO and ammonia has been investigated. Also the interaction between both water and ammonia with ...
The isomerization of neopentane has been investigated over the 0.76 wt% Pd/SiO{sub 2} catalyst. It is found that after high temperature reduction (HTR, at 873 K) the selectivity for isomerization is much higher than that after low temperature reduction (LTR, at 573 K). A variety of experiments, including kinetic, chemisorption (O{sub 2}, H{sub 2}, and CO), temperature-programmed desorption of H{sub 2}, and X-ray diffraction, showed that this selectivity enhancement cannot be interpreted in terms of H{sub 2} retention by catalyst. Instead, the formation of Pd-Si compound(s) (most probably Pd{sub 3}Si) during HTR seems immediately responsible for the catalytic behavior of HTR Pd/SiO{sub 2} catalysts. A mechanism is proposed for the Pd-SiO{sub 2} interaction in which Pd atoms (or ions) are incorporated into the silica support (via oxygen vacancies) and a new phase of palladium silicide is formed. Regeneration by an oxygen ...
Modern combined cycle power plants with natural gas as the only fuel reach efficiencies of up to 58% for electric power generation. Nevertheless the reserves of natural gas are more limited compared to the reserves of coal. Therefore possibilities should be investigated to use coal for such plants also. One concept, that combines the use of coal in a combined cycle application with high efficiencies is examined in this paper. According to this concept the exhaust gas of the gas turbine (vitiated air) is the combustion air for the pulverised coal combustion, that takes place in the bottoming steam generator. Due to the low oxygen content of the vitiated air the burnout of the coal may be incomplete. In order to avoid the incomplete combustion of the coal and the resulting decrease of the efficiency of the plant and possible emission problems, a catalyst, that converts carbon monoxide and unburnt carbon to carbon dioxide should be installed between the heating ...
In this paper, we prepared by the sol-gel method alkaline titania catalysts, doped by gelling titanium alkoxide with aqueous solutions containing potassium, rubidium or cesium chlorides. XRD patterns showed that samples annealed at 400 and 600degreeC contained a single crystalline phase, anastase. Specific surface areas were higher in samples annealed at 400degreeC (>100m2/g) than in those annealed at 600degreeC (25m2/g). The weight density of basic sites determined by CO2-TPD drastically diminished in samples treated at 600degreeC. Catalysts were tested for the self-condensation of acetone at 300degreeC; main reaction products were isomesityl oxide, mesityl oxide and mesitylene. Samples annealed at 600degreeC showed lower acetone conversion rate and low formation of mesitylene than that o...
Despite the rapid development of literature pertaining to fundamental (1-4) studies of oxidation catalysis, a general theory of heterogeneous selective oxidation catalysis explaining the selectivity behavior of different metal oxide systems has not yet been developed. Redox mechanisms have been widely invoked in the kinetic and mechanistic descriptions of selective oxidation reactions, suggesting a dynamic behavior of hydrocarbon and oxygen interactions with the catalyst surface. Nevertheless, most of the recent theoretical approaches of this subject matter (5-7) are essentially static in nature. Correlations are made with surface structure on the basis of crystallographic considerations with selectivity being related to the nature, number, bond-strength and nearness of oxygen atoms in the neighborhood of adsorption centers. The effect of the reaction medium on the configuration of the catalyst surface, and thus its influence on the reaction ...
Calcined and sulfided Ni-Mo catalysts supported on ultrastable Y zeolite (USY), NaY zeolite, mordenite, and ZSM-5 were studied by high-resolution electron transmission microscopy (HRTEM) with selected-area electron diffraction (SAED) and energy-dispersive spectroscopy (EDS). Ni and Mo oxide aggregates were rarely observed in the USY-supported Ni-Mo catalyst, indicating that most of Ni and Mo may be incorporated into USY, e.g., supercavities and possibly sodalite cages. However, there were a large number of {alpha}-NiMoO{sub 4} aggregates of different particle sizes in NaY-, mordenite-, and ZSM-5-supported catalysts, and the mordenite-supported catalyst also contained MoO{sub 3} crystals. The {alpha}-NiMoO{sub 4} may be attached to the surface of substrates as individual particles or needle aggregates, it may be disseminated into mordenite particles, or it may even form an isolated sphere (in Ni-Mo/NaY) ...
An investigation of the effect of blending of two different coals in various ratios on the hydrogenation reaction was carried out using a red mud-sulphur catalyst. Three Japanese coals and an Australian brown coal were used in the study. The conversion of the blended coals was compared with that obtained with each of the coals alone. A blend of the Yallourn brown coal and Shin-Yubari coal showed a synergism: it is considered that hydroaromatics from the Japanese coal promote the hydrogenation of the Yallourn coal. (The tables and captions in this paper are in English).
Partial oxidation of 2-propanol was carried out on AB{sub 1-x}B`{sub x}O{sub 3} (A=Ba, B=Pb, Ce, Ti; B`=Bi, Sb and Cu) type perovskite oxides. Acetone was the major product observed on all the catalysts. All the catalysts underwent partial reduction during the reaction depending on the composition of the reactant, nature of the B site cation and the extent of substitution at B site. The catalytic activity has been correlated with the reducibility of the perovskite oxides determined from Temperature Programmed Reduction (TPR) studies. (orig.)
Applying the thermochemical selectivity criterion of Hadnett et al. It is shown that the selectivity of the furan formation is not limited by a too low strength of the C-H bonds in furan when compared with the C-H bond dissociation energy in the educt molecule butadiene. In the oxidation of butadiene on a CsH{sub 2}PMo{sub 12}O{sub 40} catalyst a maximum yield of 22 mol% furan has been obtained. To improve this comparatively low furan yield oxidation activity of the catalyst must be lowered to prevent the consecutive reaction to maleic anhydride. (orig.)
This patent describes a nitrogen oxides decreasing combustion method which comprises: a first step of mixing a fuel and air with each other; a second step of bringing the mixture obtained in the first step into contact with a packed catalyst such that only catalytic combustion occurs; and a third step of adding a fresh supply of the fuel to a stream obtained from the second step to form a mixed gas and causing the mixed gas to undergo non-catalytic thermal combustion. The temperature of the packed catalyst is lower than the ignition temperature of the mixture and the adiabatic flame temperature of the mixed gas is lower than a temperature at which the nitrogen oxides occur.
The authors measured the absorption of CO{sub 2} in alkaline 0.5 M/0.5 M sodium carbonate/bicarbonate buffers containing either saccharose and sodium arsenite or saccharose and formaldehyde. Absorption enhancement increased upon increasing the concentration of either of the catalysts, but the joint action of the two was always less than the sum of their individual effects, the difference being a function of the acidities and concentrations of the catalysts and the pH of the carbonate/bicarbonate buffer solution
Red mud, and red mud activated by dissolution in hydrochloric acid and reprecipitation with ammonia, were tested as catalysts for the hydrogenation of an anthracene oil in a trickle-bed reactor. Conversion data were determined for the different polyaromatic compounds in the anthracene oil. Red mud shows appreciable catalytic activity, which is enhanced by the activation. Although both red mud and activated red mud are less active than a commercial Ni-Mo/[gamma]-alumina hydrotreating catalyst, the difference in activity is smaller when conversion to hydroaromatics instead of total conversion of reactants is considered. 20 refs., 8 figs., 3 tabs.
Hydrogenolysis reactions of a mixture of coal liquid and coal liquefaction residue were carried out using red mud - sulfur or Co-Mo/Al{sub 2}O{sub 3} catalyst. The effect of deashing treatment of coal liquefaction residue were also investigated. Notable synergistic effects such as the increase of n-hexane soluble and the decrease of dichloromethane insoluble were observed only with the hydrogenolysis of the basic fraction of coal liquid and nondeashed coal liquefaction residue using red mud-sulfur catalyst. 4 refs., 2 figs., 2 tabs.
Light microscopy was used to analyze the effects of added catalyst at different conditions (temperature and reaction times) in liquefaction testing of a low pyritic sulfur bituminous coal. Quantitative changes in vitrinite/vitroplast reflectance of coal and liquefaction residues were shown to be useful markers in analyzing and understanding the role of catalyst during the initial stage of coal particle hydrogenation. Lower reflectance values corresponded to increased conversions up to about the 60 min and 375{degrees}C experimental conditions. Microscopical observation of liquefaction residues also revealed the presence of `wall scales` of varying width.
The Cu/CeO{sub 2} and Cu/Cr/CeO{sub 2} catalysts synthesized using the impregnation method were employed to investigate the selective reduction of NO{sub x} with C{sub 3}H{sub 6} at 673.15K and 1atm. The activity of CeO{sub 2} was greatly induced by loading 4wt.% of Cu onto the bare support. The presence of C{sub 3}H{sub 6} was a crucial factor for elevating the NO{sub x} conversion under lean conditions. The modification of the optimal Cu(4)/CeO{sub 2} catalyst with 3wt.% of Cr steadily improved the performance of the catalysts. Both the optimal Cu(4)/CeO{sub 2} and Cu(4)/Cr(3)/CeO{sub 2} catalysts were characterized using XRD, SEM and TPR-H{sub 2}. The co-existence of CuO, Cr{sub 2}O{sub 3} and CuCr{sub 2}O{sub 4} was believed to grant the promising performance of the Cu(4)/Cr(3)/CeO{sub 2} catalyst in SCR-HC under net oxidizing conditions.
Among the items of the Sunshine Project in fiscal 1981 for development of a solvent extraction and liquefaction plant, this paper describes the achievements in developing secondary hydrogenation. A small continuous hydrogenation device equipped with three reaction columns that can be filled with catalyst of 50 cc, and a dedicated testing room were designed, and orders were placed with manufacturers. The fabrication, assembly, delivery, installation, piping and wiring were all completed. The device passed a completion inspection based on the high-pressure gas safety assurance law in December 1981. After leakage due to gas and material oil was checked, a trial operation was performed, and verified of normal operation. A screening test was carried out on three kinds of commercially available and prototype catalysts before testing the SRC containing material for studying the secondary hydrogenation. The circulating solvent having a boiling point ...
The trend towards more effective use of fossil fuels and reduced environmental pollution represents a major task of improvement within the refinery processes. The highly isomerized and high octane paraffins produced from isobutane and light olefins by alkylation fulfill all the requirements for reformulated gasoline. This doctoral thesis discusses new catalyst systems because of their potential in alkylation. A slurry reactor apparatus for solid-acid catalysed isobutane/butene alkylation was developed and used to investigate the performance of various heterogeneous catalysts. The selected materials were mainly zeolite types with faujasite structures. The samples were characterized by various methods before alkylation. In general, the order of decreasing catalyst activity after 3 h of reaction at 80{sup o}C was found to be: H-EMT >> H-FAU, dealuminated H-FAU >> NS.500, TA-Y, CeY-98 > Nafion-H. The order of ...
The current work continues a project completed in 1999 by ReMaxCo Technologies in which a novel, microwave based, VLS Silicon Carbide Fibrils concept was verified. This project continues the process development of a pilot scale commercial reactor. Success will lead to sufficient quantities of fibrils to expand work by ORNL and others on heat exchanger tube development. A semicontinuous, microwave heated, vacuum reactor was designed, fabricated and tested in these experiments. Cylindrical aluminum oxide reaction boats are coated, on the inner surface, with a catalyst and placed into the reactor under a light vacuum. A series of reaction boats are then moved, one at a time, through the reactor. Each boat is first preheated with resistance heaters to 850 C to 900 C. Each reaction boat is then moved, in turn, to the microwave heated section. The catalyst is heated to the required temperature of 1200 C to 1300 C while a mixture of MTS (methyl ...
In-situ methods are well known as powerful tools in studying catalyst formation processes, their solid state properties under working conditions and the interaction with the feed, intermediates and products to reveal reaction mechanisms. This paper gives a short overview on results of intense studies using in-situ techniques to reveal VPO catalyst generation processes, interaction of educts, intermediates and products with VPO catalyst surfaces and mechanistic insights. Catalytic data of the ammoxidation of toluene on different VPOs complete these findings. The precursor-catalyst transformation processes were preferently investigated by in-situ XRD, in-situ Raman and in-situ ESR spectroscopy. The interaction of aromatic molecules and intermediates, resp., and VPO solid surfaces was followed by in-situ ESR and in-situ FTIR spectroscopy. Mechanistic information was mainly obtained using in-situ FTIR ...
The overall objective of this project was to develop a new approach for the direct liquefaction of coal to produce an all-distillate product slate at a sizable cost reduction over current technology. The approach integrated coal selection, pretreatment, coal swelling with catalyst impregnation, liquefaction, product recovery with characterization, alternate bottoms processing, and a technical assessment including an economic evaluation. Heterofunctional solvents were the most effective in swelling coals. Also solvent blends such as isopropanol/water were more effective than pure solvents alone. Impregnating slurry catalysts simultaneously during coal swelling showed that better uptake was achieved with nonswelling solvent and higher impregnation temperature. Some enhancement in initial coal conversion was seen liquefying SO{sub 2}-treated Black Thunder coal with slurry catalysts, and also when hydrogen donor liquefaction ...
In the third quarterly report adsorption of heavy metals ions such as Cu(II) and Cr(VI) onto soils drawn from the laboratory-type wetland was shown to be weak. Secondly, it was shown that modified-clays did adsorb Cr(VI) ions strongly at pH 4.5. Further, studies on the pH dependence of the adsorption of {beta}-naphthoic acid, (NA), a well-documented contaminant in many oil and gas well waste waters onto modified-clays were undertaken and it was shown that uptake of NA by modified-clays was of the high affinity type at pH 4.5 and 7.0, but weak at pH 9.0. Adsorption of heavy metal ions, Cu{sup 2+}, and Cr(VI) onto algae, a proposed wetland amendment, was carried out and the results were presented and discussed in the fourth quarterly report. Uptake of NA by the soil component of the laboratory-type wetland was monitored as a function of pH. This quarterly report presents results from studies on the uptake of phenol and ...
This report summarizes the objectives, background, technical progress, and status of ANL electric vehicle battery R&D tasks for DOE-EHP during the period of January 1 through March 31, 1991. The work is organized into the following six task areas: Project management; battery systems technology; lithium/sulfide batteries; advanced sodium/metal chloride battery; aqueous batteries; and EV Battery performance/life evaluation.
We propose a scheme with potential experimental realization to generate 'polarization' entanglement between two atomic ensembles and show one of the applications - a novel secure communication allowing asymptotically key distribution and quasisecure direct communication. The scheme involves laser manipulation of atomic ensembles, adjustable quarter- and half-wave plates, beam splitters, polarizing beam splitters and single-photon detectors, and well fits the status of the current experimental technology.
This journal includes all formal reports in the NUREG series prepared by the NRC staff and contractors, as well as proceedings of conferences and workshops. The entries in the compilation are indexed for access by title and abstract, contractor report number, personal author, subject, NRC organization, contractor, and licensed facility.
Research is being carried out in this project in two areas which are of interest to ongoing investigations at the Pittsburgh Energy Technology Center (PETC). They are: (a) thermal behavior of slurry reactors used for indirect coal liquefaction; and (b) coal liquefaction under supercritical conditions. The current status of each of these tasks is summarized in this report. 76 refs., 23 figs., 6 tabs.
Research is being carried out in this project in two areas which are of interest to ongoing investigations at the Pittsburgh Energy Technology Center (PETC). They are: (1) behavior of slurry reactors used for indirect coal liquefaction, and (2) coal liquefaction under supercritical conditions. The current status of each of these tasks is summarized in this report.
Task 13 (a) was approved on December 21, 2001. Minimal work was performed for the quarter during the approval process. Laboratory and equipment facilities have been maintained in anticipation of the work to be done. The PI communicated with DOE and Estonia researchers during this period, providing advice and direction for the startup of the Estonia research, and preparing a Draft Teaming Agreement. The PI participated in an industrial liaison meeting with DOE personnel. This meeting is expected to lead to formal cooperation between industry and government.
The purpose of this project is to demonstrate targeted infill and extension drilling opportunities, better determinations of oil-in-place, methods for improved completion efficiency and the suitability of waterflooding in certain shallow-shelf carbonate reservoirs in the Williston Basin, Montana, North Dakota and South Dakota. Results of seismic surveys are presented.
...] 2002, Volume 2002, Issue 2-Summer 1-16 A Descriptive Analysis of the Irish Housing Market by Duffy, David [Downloadable!] 2002, Volume 2002, Issue 1-Spring 1-13 Interpreting Recent Developments in the Economy and Labour Market by Sexton J. J. [Downloadable!] 2001, Volume 2001, Issue 4-December 1-4 Budget 2002: Analysis of the Distributional Impact by Callan, Tim & Keeney, Mary ...
This program is concerned with the development of an advanced method for the separation of hydrogen sulfides from coal gas. The process utilizes an electrochemical membrane which removes hydrogen sulfide without cooling the gas and with negligible pressure loss through the separator.
Projects associated with this grant for studying hazardous materials in aquatic environments of the Mississippi River Basin are reviewed and goals, progress and research results are discussed. New, one-year initiation projects are described briefly.
Real-time horizon sensing on continuous mining machines is becoming an industry tool. Installation and testing of production-grade Horizon Sensor (HS) systems continued this quarter at Monterey Coal Company (ExxonMobil), Mountain Coal Company West Elk Mine (Arch), and Ohio Valley Coal Company (OVC). Monitoring of system function, user experience, and mining benefits is ongoing. All horizon sensor components have finished MSHA (U.S.) and IEC (International) certification.
This report covers the period from October 1, 1992 to March 1, 1993. The overall goals of the program task are to provide a final synthesis of six deep seismic reflection profiles and other geological and geophysical data from the southern Washington Cascades region where a probable extensive deep sedimentary basin has been discovered. This deep sedimentary basin is hypothesized from geological, regional magnetotelluric (MT), gravity, magnetic , and seismic reflection data as described in the American Association of Petroleum Geologists (AAPG) article by Stanley and others (1992). This report analyzed three seismic reflection profiles acquired by the Morgantown Energy Technology Centers in combination with the extensive MT and other data to outline a probable geological model for a thick conductive section of rocks in the southern Washington Cascades (called the Southern Washington Cascades conductor, SWCC). Earlier MT models suggested that the section consisted of an east-dipping ...
Contacts with researchers, manufacturers, and users of enhanced heat transfer equipment are summarized. The Technical Literature file and the Patent File continue to be updated; the Patent File is the source for a patent technology report now in draft form. Application studies on a rationally-based friction correlation for internally-finned tubes and on the evaluation of candidate tube-side enhancements for OTEC applications are reported. The technology study on enhancement of spray evaporation is also discussed.
In this first quarterly technical report for DOE Contract No. DE-AC22-87PC79654, a description of the background, technology, and application is provided. The design and fabrication of advanced combustion chambers were completed during this period. Initial testing on both the bare metal and refractory lined advanced chambers were initiated. The units were tested initially with gas but primarily with coal. A Pittsburgh No. 8 pulverized coal was used for these test activities. Both advanced chambers pulsed well.
Research programs in coal liquefaction are briefly discussed. The following projects are addressed: coal desulfurization by bioprocessing; materials characterization study of liquefaction processes; novel approaches to catalysis in coprocessing and in direct coal liquefaction; liquefaction research in pyrolysis catalysis, and coal dissolution; enhanced reactivity and selectivity in coal liquefaction and coprocessing systems. (CBS)
This quarterly report covers the period from January 1, 2005 through March 31, 2005. It covers: technical development, permitting status, engineering status, construction status, operations summary and marketing support activities for this period. Plant startup is still continuing. Testing of admixtures to enhance extrusion and SDA wetting is continuing. Efforts are underway to improve plant availability.
ERDA's coal liquefaction program is reviewed, especially the progress with several pilot plant operations. Other items involve the possible recovery of organic chemicals from coal liquids, the filtration of coal liquids, some experiments on hydrogenation and carbonization, and renovation of the Cresap materials and equipment test facility. (LTN)
In addition to an executive summary and glossary, the following sections are included: Clean Boiler Fuel Demonstration Plant; Development of Coal Feeders for Coal Gasification Operations; Development of a Continuous Dry Coal Screw Feeder; Coal Feeder Development Program; Engineering and Technical Support; Technical Assistance Services; and Conceptual Design for an Advanced Coal Liquefaction Commercial Plant. (EJH)
In addition to an executive summary and glossary, the following sections are included: Clean Boiler Fuel Demonstration Plant; Development of Coal Feeders for Coal Gasification Operations; Development of a Continuous Dry Coal Screw Feeder; Coal Feeder Development Program; Engineering and Technical Support; and Technical Assistance Services. (EJH)
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... 1 (2008) Algorithms - Open Access Journal Algorithms (ISSN 1999-4893; CODEN: ALGOCH), an open access journal of computer science, theory, methods and interdisciplinary applications, data and information systems, software engineering, artificial intelligence, automation and control systems, is published online quarterly by MDPI. - free for readers, with low publishing fees paid by authors or their institutions High visibility: indexed in leading indexing and abstracting databases....
The Project was started August 1, 1992. During these first two months, the Project Management plan was issued and approved during discussions at the Pittsburgh Energy and Technology Centre. Feed materials for the experimental work (with the exception of the second solvent) have been received. The analytical work up of these feed materials has been completed, and autoclave stability tests with the solvent and solvent fraction have been performed and analyzed. The Project is proceeding on schedule.
Programs in coal research by the Pittsburgh Energy Technology Center are discussed. Topics include: Coal Science and Chemistry, Coal Liquefaction, Alternative Fuels, Coal Preparation, Combustion, MHD Program, Flue Gas Cleanup, Environmental Coordination, and Technology Transfer. (CBS)
Studies in advanced coal research are presented. Included are the following: coal science programs; coal preparation and combustion kinetics; advanced technology in liquefaction, including direct and indirect liquefaction; alternative fuels; advanced combustion technology; flue gas cleanup; environmental coordination, technology transfer, and clean coal demonstration program. (CBS)
We present differential scanning calorimetry (DSC), X-ray diffractometry, in situ Moessbauer spectroscopy (MS), and transmission electron microscopy (TEM) studies in Metglas ribbons subjected to different heat treatments. The temperature evolution of the hyperfine field H_h_f(T) and the Curie temperature (T_c) of the amorphous phase are determined. The magnetic field originally present in the amorphous phase has a 'normal' behavior, in the sense that it can be described by the Weiss molecular field theory. The total angular momentum of the iron atoms turns out to be 5/2 and this implies Fe"3"+ in which the electronic spins are uncoupled. When the samples are maintained near T_c (#approx#673 K), three new magnetic phases are detected in the Moessbauer spectra, indicating an onset of a crystallization process well below the first crystallization temperature (T_X_1), as determined by DSC (#approx#820 K). The magnetic behavior of these phases is also described by ...
We succeeded in synthesizing a new cubic intermetallic compound PrCu_4Ag in a fcc structure. Measurements of X-ray diffraction, magnetic susceptibility, magnetization, specific heat, electrical resistivity, thermal expansion, and elastic constants have been performed on single crystals of PrCu_4Ag. A maximum value of #chi#(T) with a corresponding peak in C(T) suggests that an antiferromagnetic phase transition occurs at T_N=2.4 K, where a sudden decrease in #rho#_4_f(T) and a sharp peak in the thermal expansion coefficient #alpha#(T) were observed. Characteristic Curie-type softening was observed in the temperature dependence of the transverse mode for (C_1_1 - C_1_2)/2 and C_4_4 from 70 K down to T_N, which implies that the crystalline electric field (CEF) ground state is the magnetic triplet #GAMMA#_5. The anisotropic properties in M(T,H) and C(T,H) are studied when the external magnetic field is applied in the <100>, <110>, and <111> ...
The oxide colloidal route, developed in the laboratory for mono-metallic catalysts, consists in preparing a metallic oxide hydro-sol which leads to the supported catalyst after deposition onto a support and an activation stage. In this work, this method has been adapted to the preparation of alumina supported bimetallic Pd-Sn catalysts to determine its interest for the control of the properties of the bimetallic phase (size, composition and structure). In the preliminary study concerning tin oxide sols, SnO{sub 2} (size=2,3 nm) and Sn{sub 6}O{sub 4}(OH){sub 4} (size = 25 nm) nano-particles were synthesized by neutralization respectively for tin(IV) and tin(H). The control through the pH of the aggregation of the PdO and SnO{sub 2} particles revealed that increasing oxide solubility promotes integral re-dispersion of the oxide particles. To synthesize oxide bimetallic sols, three strategies were defined. Copolymerization ...
The behaviour of two different catalytic precursors based on iron (FeSO{sub 4}.7H{sub 2}O) and Fe{sub 2}O{sub 3} in direct hydroconversion of two coals are studied in this paper. Coal itself was the catalytic support of the dispersed iron sulfide (from iron sulfate); when the catalyst precursor was iron oxide (from red mud), coal and catalyst were directly mixed as powders. The reaction conditions were: 10 MPa (H{sub 2}, cold) initial pressure, 30 min, and reaction temperatures of 300, 350, 400, and 425{degree}C, reaching 450 and 500{degree}C for the high-rank coal. The results from Moessbauer spectroscopy demonstrate that pyrite in all the runs, inherent to coal or added as catalyst precursor, is converted into pyrrhotite to a variable extent according to the previous iron distribution and the iron chemical state in the catalyst precursors as well as the CS{sub 2} addition. Important chemical and ...
Flowsheets for the dissolution of aluminum-clad spent nuclear fuel have been proposed using 0.002 M mercuric nitrate catalyst in 5 to 6 M nitric acid. Previous calculations for flammable gas control during the dissolution of spent nuclear fuel have been extended to cover a range of dissolver purge rates from 40 to 55 scfm. A range of dissolver solution volumes from 12000 to 15000 liters were considered for the large H-Canyon dissolver (6.4D). Depending on the purge rate, anywhere from four to six bundles of MURR fuel can be initially charged to the dissolver (6.4D). For successive charges where the dissolver solution already contains 0.002 M mercury catalyst and the dissolved aluminum from five bundles of MURR fuel, five to nine bundles of additional fuel can be charged depending on the purge rate and the dissolver solution volume. Similar calculations have been performed for the small H-Canyon dissolver (6.1D) for solution volumes that ranged ...
This report presents the operating results for Run 245 at the Advanced Coal Liquefaction R and D Facility in Wilsonville, Alabama. This run was made in an all-distillate Integrated Two-Stage Liquefaction (ITSL) mode using Illinois 6 coal from the Burning Star mine. The primary run objective was to obtain steady-state ITSL performance by replacing spent HTR reactor catalyst with fresh, sulfided catalyst. Secondary objectives were to maintain an all-distillate (minimum resid production) product slate and to demonstrate the effects of catalyst addition on the net gas production and hydrogen consumption. Run 245 began on 7 November, 1983, and continued through 12 February, 1984. During this period, 179.0 tons of coal was fed in 2045 hours of operation. Eight special product workup material balances were defined, and the results are presented herein. 6 references, 28 figures, 20 tables.
Sulfated zirconia (SO4-ZrO2) catalysts, prepared with three different sulfur loading contents (0.75%, 1.8% and 2.5%) at two calcination temperatures (500degreeC and 700degreeC), were tested for use in the transesterification of purified palm oil (PPO) and the esterification of palm fatty acid (PFA) in near-critical and super-critical methanol. Techniques including BET, XRD, NH3- and CO2-TPD revealed that the sulfur content and calcination temperature strongly affects the catalyst base-acid site, specific surface area, average pore size, phase structure, and thus the catalytic reactivity. The most suitable sulfur loading content was found to be 1.8% and the optimum calcination temperature 500degreeC. The results show that the use of SO4-ZrO2 reduces esterification reaction times, the amount...
Essential to today's modern refineries and the gasoline production process are fluidized catalytic cracking units. By using a computational fluid dynamics (CFD) code developed at Argonne National Laboratory to simulate the riser, parametric and sensitivity studies were performed to determine the effect of catalyst inlet conditions on the riser hydrodynamics and on the product yields. Simulations were created on the basis of a general riser configuration and operating conditions. The results of this work are indications of riser operating conditions that will maximize specific product yields. The CFD code is a three-dimensional, multiphase, turbulent, reacting flow code with phenomenological models for particle-solid interactions, droplet evaporation, and chemical kinetics. The code has been validated against pressure, particle loading, and product yield measurements. After validation of the code, parametric studies were performed on various parameters such ...
Hydrogenation of carbon monoxide at 101.3 kPa has been studied over a series of ion-exchanged Ru catalysts supported on NaX, NaY, KL, Na mordenite, and HY zeolites. The type of zeolite had pronounced effects on the activity and selectivity of the Ru. The specific activity would appear to be related to the dispersion of reduced ruthenium in the zeolite. Methane selectivity, however, seems to be strongly influenced by the type and concentration of alkali cations remaining in the ion-exchanged zeolite. These cations appear to promote chain growth much as traditional alkali promoters would, though perhaps more indirectly. Due to bifunctional properties of the zeolite-supported catalysts, a significant fraction of C/sub 4/ was in the form of isobutane. Formation of isobutane seems to be related to either the Si/Al ratio in the zeolites or the concentration of the remaining alkali cations, but not to the OH concentration. In addition, H/sub 2/ ...
For the coal liquefaction, improvement of liquefaction conditions and increase of liquefied oil yield are expected by suppressing the recombination through rapid stabilization of pyrolytic radicals which are formed at the initial stage of liquefaction. Two-stage liquefaction combining prethermal treatment and liquefaction was performed under various conditions, to investigate the effects of reaction conditions on the yields and properties of products as well as to increase liquefied oil yield. Consequently, it was found that the catalyst contributes greatly to the hydrogen transfer to coal at the prethermal treatment. High yield of n-hexane soluble fraction with products having low condensation degree could be obtained by combining the prethermal treatment in the presence of hydrogen and catalyst with the concentration of slurry after the treatment. This was considered to be caused by the synergetic effect between the improvement of ...
A process is described for the selective oxidation of ammonia to nitric oxide in about 90% or greater yield with a minimum of nitrogen or dinitrogen oxide (N/sub 2/O) as by-products, comprising: (1) contacting gaseous ammonia in an oxygen containing gas optionally with an inert gaseous diluent with a mixed metal perovskite catalyst of the general formula: ABO/sub 3/, wherein: A is selected from the alkali, alkaline earth, lanthanide, or actinide metals or a mixture of these metals having a relatively large ionic, radius, and B is selected from an element or a combination of elements selected from Groups IB, IVB, VB, VIB, VIIB, or VIII of the Periodic Table, wherein the perovskite phase of the catalyst has an equilibrium partial pressure of oxygen at 1000/sup 0/C of greater than about 10/sup -15/ bar; and (2) heating the reactants of step (1) at greater than about 500/sup 0/C under conditions of 10 to 100,000 hr/sup -1/ hourly space velocity.
A process is described for the selective oxidation of ammonia to nitric oxide in about 90% or greater yield with a minimum of nitrogen or dinitrogen oxide (N/sub 2/O) as by-products, comprising: (1) contacting gaseous ammonia in an oxygen containing gas optionally with an inert gaseous diluent with a mixed metal perovskite catalyst of the general formula: ABO/sub 3/, wherein: A is selected from the alkali, alkaline earth, lanthanide, or actinide metals or a mixture of these metals having a relatively large ionic, radius, and B is selected from an element or a combination of elements selected from Groups IB, IVB, VB, VIB, VIIB, or VIII of the Periodic Table, wherein the perovskite phase of the catalyst has an equilibrium partial pressure of oxygen at 1000"0C of greater than about 10/sup -15/ bar; and (2) heating the reactants of step (1) at greater than about 500"0C under conditions of 10 to 100,000 hr/sup -1/ hourly space velocity.
Catalytic reactions of 3-methylpentane and 2,3-dimethylbutane on HY, amorphous silica-alumina, and HZSM-5 have been studied at 500{degree}C. Both kinetic phenomena and product selectivities have been reported. Cracking reactions an HZSM-5 can be attributed to initiation through protonation occurring at Bronsted sites. Bimolecular processes leading to chain reaction via hydride transfer are restricted within the narrow pore pentasil zeolite. On HY and amorphous silica-alumina, initiation of cracking also occurs at Bronsted sited. No direct evidence was found for participation of Lewis acid sites on the catalyst framework itself. Following initiation, reactions on these catalysts are accelerated through a chain process occurring at Lewis sites generated by adsorption of product olefins at Bronsted sites. The resulting change in the dominant cracking mechanism is reflected in the product selectivity, illustrated here by a falling off in formation ...
The selective catalytic reduction of nitric oxide by methane over copper ion-exchanged natural zeolites was investigated in a packed-bed tubular reactor. The catalytic activity of Cu-N and Cu-H-N catalysts was confirmed as NO, CH{sub 4}, and O{sub 2} displayed very little reaction in the absence of any catalyst and zeolite without ion exchange was totally inactive. A maximum NO conversion of 33% at 650 C for Cu-N-66 was achieved with 2% NO and 1% CH{sub 4} and a contact time of 0.9 g s/cm{sup 3}, but the introduction of 2% O{sub 2} reduced the NO conversion to only 12%. Ion exchange for the H-form prior to copper ion exchange was essential for oxygen to promote catalytic activity over the temperature range 250--650 C, with a maximum conversion of 30% at 450 C with O{sub 2} present. The direct reduction of NO by methane was ruled out as a possible reaction pathway.
Our goal was a process to convert methane to higher hydrocarbons oxidatively, since this circumvents thermodynamic yield limits of a strictly degydrogenative process. Keller and Bhasin converted thermodynamic yield limits of a strictly dehydrogenative process. Keller and Bhasin converted methane to higher hydrocarbons by using metal oxides as oxidants, without co-fed oxygen. They stated that selectivity is necessarily poor if gaseous oxygen is present. Jones and Sofranko have also used reducible metal oxides as oxidants in a group of their parents, but later used some of those materials with continuous O{sub 2} feed without much loss of selectivity. Baerns, Lunsford and Otsuka have shown that high selectivity could be possible with co-fed O{sub 2} at least for low O{sub 2} partial pressures, over PbO-A1{sub 2}O{sub 3}, Li-MgO and rare earths. The performance of a group of multicomponent oxide catalysts, containing lead and magnesium oxides, for oxidative conversion ...
Ionic liquids can enhance the activity, selectivity, and stability of enzyme catalysts. Enzymes and ionic liquids as catalysts are seen as a more environmentally friendly technology than the use of traditional catalyst materials in biofuels production. This study investigated the lipase catalyzed esterification reaction for biodiesel production in the presence of the ionic liquid BMIM PF{sub 6}. Methyl acetate was used as the acyl acceptor. A titremetric assay was conducted to measure the activity of the lipase with various amounts of ionic liquid. Reaction parameters were investigated in order to determine their effects on biodiesel conversion. An 80 per cent overall methyl oleate biodiesel yield was successfully produced in the presence of the ionic liquid. The ionic liquid improved lipase activity as well as overall biodiesel yield. Results also showed that the addition of the ionic liquid facilitated the separation of ...
ObjectivesThe overall aim of this work is to use an in-situ FTIR probe to investigate selected heterogeneous catalysts in industrially relevant organic reactions. This approach will be broadly applicable to the UK fine chemical manufacturing base.~%~~%~The project has the following specific objectives:~%~~%~- To demonstrate and develop the use of an in-situ FTIR probe in a batch reactor at elevated temperatures (eg greater than 100 deg C) to monitor reactant usage and product formation.~%~~%~- To validat [continued...]DescriptionThis proposal concerns the in-situ study of catalytic processes and reaction kinetics. The catalysts concerned are microporous materials, such as, zeolites, containing pores and cavities of molecular dimensions. These catalysts constitute crystal reactors on a nanometer scale that are selective on a size and shape basis for organic molecules used ...
Taiheiyo coal deashed using acid treatment and loaded with potassium or calcium was hydro-cracked under gaseous phase to discuss effects of these metals on liquefaction reaction. In addition, the loaded coal was added with red mud catalyst to examine effects of the addition. The loaded potassium has a softening power, and particularly the potassium adsorbed into surface and micropores in the coal decomposes selectively HI-BS and BI-PS and generates gas and HS. On the other hand, potassium deposited on coal surface promotes direct gas production from the coal. Irrespective of its loading modes, calcium has a catalytic nature to produce HI-BS selectively. Calcium also acts to impede decomposition of HI-BS into HS. Adding red mud catalyst to potassium loaded coal increases the inversion rate and the liquefaction yield, and most of the increase is accounted for by HI -BS, and BI-PS. When red mud catalyst is added to calcium ...
Hydrogenolysis of quinoline was carried out using red mud catalyst at 390{degree}C and 450{degree}C to study denitrogenation reaction in the first stage liquefaction of coal. Quinoline was decomposed to ammonia via 1-THQ or hydrogenated to 5-THQ. The reaction rate constants obtained at 390{degree}C were k{sub 1} = 1.83 {times} 10{sup {minus}6}, k{sub 2} = 1.16 {times} 10{sup {minus}7}, and k{sub 3} = 3.24 {times} 10{sup {minus}7} mol {center dot} dm{sup {minus}3} {center dot} min{sup {minus}1} {center dot} g {center dot} {sup {minus}1}. The rate constants for hydrogenation of quinoline were in the order of hexadecane > trans-decalin > 1-methylnaphthalene. Ratios of equilibrium adsorption constant between trans-decalin and quinoline and between 1-methylnaphthalene and quinoline were found to be 0.055 and 0.155 respectively. The equilibrium constant of phenol to red mud catalyst adsorption was calculated to be 3 times of that of quinoline, ...
Carbon supported catalysts can lose their activity over a period of time due to the sintering of the nanometer-sized catalyst particles. The sintering of metal clusters on carbon supports can occur due to the weak interaction between the metal and the support and also due to the corrosion of carbon, especially in fuel cell electrocatalysts. The sintering may be reduced by increasing the interaction between the metal and the support and also by increasing the corrosion resistance of carbon supports. In an effort to mitigate the growth of the nanoparticles, carbon-substituted boron defects were introduced in the carbon lattice. The interaction between the Pt nanoparticles on the pure and boron-doped carbon supports was examined using X-ray photoelectron spectroscopy (XPS). The results indicate that the interaction between the Pt nanoparticles and the boron-doped carbon support was slightly stronger than the interaction between the Pt ...
Cyclopropane isomerization to propylene over various Eu[sup 3+] loadings in NaX zeolite have been studied by measurements of steady-state and transient kinetics and by Fourier transform infrared spectroscopy. As Eu[sup 3+] loading increases, the rate of deactivation increases, the conversion increases, apparent activation energies are lowered, and Bronsted acid site strength and amounts increase. Apparent activation energies of 13-15 kcal/mol for propylene formation have been observed for these systems, consistent with literature reports for other metal supported heterogeneous catalyst systems. Deactivation studies have shown that activity can be restored by heating in He at 380[degrees]C between various temperature runs, and that gases desorbed during regeneration are predominantly propylene. Poisoning studies of Bronsted sites with Na vapor lead to deactivation of these catalysts. A reaction mechanism scheme based on [pi] allyl intermediates ...
The objective of our research was to obtain fundamental information regarding the functional dependence of the diffusion coefficient of coal molecules on the ratio of molecule to pore diameter. That is, the objective of our study was to examine the effect of molecule size and configuration on hindered diffusion of coal macromolecules through as porous medium. To best accomplish this task, we circumvented the complexities of an actual porous catalyst by using a well defined porous matrix with uniform capillaric pores, i.e., a track-etched membrane. In this way, useful information was obtained regarding the relationship of molecular size and configuration on the diffusion rate of coal derived macromolecules through a pore structure with known geometry. Similar studies were performed using a pellet formed of porous alumina, to provide a link between the idealized membranes and the actual complex pore structure of real catalyst extrudates. The ...
A magnetic core/shell Fe3O4/FeMnOx catalyst was prepared by a simple oxidation-precipitation method. The catalyst was characterized by X-ray diffraction, transmission electron microscope, X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy, thermogravimetric analysis and cyclic voltammetry. The characterization studies verified that Fe3O4 core was coated with a layer of Fe-Mn oxide. The Fe3O4/FeMnOx was found to be an effective and stable heterogeneous catalyst for the discoloration of methylene blue (MB) in aqueous solution by H2O2. The high catalytic activity is due to the FeMnOx shell, which not only increased the surface hydroxyl groups, but also enhanced the interfacial electron transfer. The discoloration of MB could be due to the decomposition of H2O2 into ?OH ...
Since natural pyrite is easy to obtain and cheap as coal liquefaction catalyst, it is to be used for the 150 t/d scale NEDOL process bituminous coal liquefaction pilot plant. NEDO and NCOL have investigated the improvement of catalytic activity of pulverized natural pyrite for enhancing performance and economy of the NEDOL process. In this study, coal liquefaction tests were conducted using natural pyrite catalyst pulverized by dry-type bowl mill under nitrogen atmosphere. Mechanism of catalytic reaction of the natural pyrite was discussed from relations between properties of the catalyst and liquefaction product. The natural pyrite provided an activity to transfer gaseous hydrogen into the liquefaction product. It was considered that pulverized pyrite promotes the hydrogenation reaction of asphaltene because pulverization increases its contact rate with reactant and the amount of active points on its surface. It was ...
This topical report presents data and results obtained from the hydrogen microautoclave. The autoclave has been used to test for the quality of hydrotreater residue product and hydrotreater catalyst activity. Data obtained from Run 242 and the first part of Run 243 is presented in a convenient format and conclusions based upon this data are summarized. Some of the topics discussed in this report are the following: development and description of procedures for the catalyst and hydrotreater residue, the significance of test results and their meaning, and the relationship of test results to process performance. 7 references, 13 tables, 22 figures.
In order to avoid the use of catalysts in the process of auto-thermal reforming, it is possible to adopt a running at high temperature. In this study are presented the results of simulations of an auto-thermal/recuperator hybrid reforming system; these results are obtained with the oxidation model of alkanes developed by Ranzi and Faravelli. An isothermal configuration at high temperature improves the hydrogen yield and avoids the formation of soots. The analysis of the powers to be furnished to assure such an experimental mode, and the global approach of the fuel cell system show that the management of the heat exchanges is a key parameter in this process. (O.M.)
The potential use of uranium in the field of catalysis is presented in the first part of this paper. Numerous applications of uranium binary oxides, as well as mixed oxides, are reviewed with a special emphasis on the role of U-Sb-O catalysts in selective oxidation (and ammoxidation) processes. Attempts are made to correlate the electronic structure of uranium, and especially the role that 5f electrons play in bonding, with its promising catalytic properties. In the second part, new data are given for uranium-bismuth mixed oxides in the catalytic oxidation of CO by O_2. Kinetic tests performed in a flow microreactor allow a mechanism to be proposed that involves the direct participation of lattice oxygen of the catalyst in the chemical process (redox mechanism). The high activity can be related to the ability of uranium to change reversibly its oxidation state. (author).
In this paper, steady-state isotopic transient kinetic analysis (SSITKA) is used to study two model reactions, CO oxidation and CO-NO reactions, on a typical formulation of a three-way auto-catalyst. Under steady-state conditions, abrupt switches in the isotopic composition of CO ("1"2C"1"6O/"1"3C"1"8O) were carried out to produce isotopic transients in both labeled reactants and products. Along with the determination of the average surface lifetimes and concentrations of reaction intermediates, an analysis of the transient responses along the carbon reaction pathway indicated that the distribution of active sites for the formation of CO_2 was bimodal for both reactions. Furthermore, relatively few surface sites contributed to the overall reaction rate.
Natural gas is a promising alternative fuel to meet strict engine emission regulations in many countries. Natural gas engines can operate at lean burn and stoichiometric conditions with different combustion and emission characteristics. In this paper, the operating envelope, fuel economy, emissions, cycle-to-cycle variations in indicated mean effective pressure and strategies to achieve stable combustion of lean burn natural gas engines are highlighted. Stoichiometric natural gas engines are briefly reviewed. To keep the output power and torque of natural gas engines comparable to those of their gasoline or Diesel counterparts, high boost pressure should be used. High activity catalyst for methane oxidation and lean deNOx system or three way catalyst with precise air-fuel ratio control str...
The potential use of uranium in the field of catalysis is presented in the first part of this paper. Numerous applications of uranium binary oxides, as well as mixed oxides, are reviewed with a special emphasis on the role of U-Sb-O catalysts in selective oxidation (and ammoxidation) processes. Attempts are made to correlate the electronic structure of uranium, and especially the role that 5f electrons play in bonding, with its promising catalytic properties. In the second part, new data are given for uranium-bismuth mixed oxides in the catalytic oxidation of CO by O/sub 2/. Kinetic tests performed in a flow microreactor allow a mechanism to be proposed that involves the direct participation of lattice oxygen of the catalyst in the chemical process (redox mechanism). The high activity can be related to the ability of uranium to change reversibly its oxidation state.
X-ray photoelectron spectroscopy measurements indicate that the Ce{sup 3+} like fraction in {gamma}-Al{sub 2}O{sub 3} supported CeO{sub 2} can be decreased by the incorporation of La{sup 3+}. If La{sup 3+} is incorporated into the {gamma}-Al{sub 2}O{sub 3} before CeO{sub 2} is added, a higher CeO{sub 2} dispersion and a greater range of reversible reducibility of the CeO{sub 2} may also be obtained. These changes offer potential for improvement in the oxygen storage capacity provided by CeO{sub 2} in three-way catalysts. The actual effect of La{sup 3+} incorporation on the activity and durability of a Pt catalyst is assessed by a combination of temperature programmed reduction and flow reactor measurements.
Hydrotalcites with different Al/Al+Mg ratios, and prepared at different pH and different aging temperatures of the gel were used as precursors of Mg-Al mixed oxides, and their textural and physicochemical properties were determined. A complete reaction network for the isopropanol decomposition on these catalysts has been established, and it is shown that the concentration of acetone in the products cannot always be used for a direct estimation of the rate of dehydrogenation. The Al/Al+Mg ratio for which the maximum in activity is obtained depends on the base strength needed for each particular reaction. For dehydrogenation of isopropanol, this is found at Al/Al+Mg [approx] 0.25. 36 refs., 10 figs., 2 tabs.
Nowadays, the studies are focused on the search of better electrocatalysts that promote the complete oxidation of ethanol/bioethanol to CO2. To that end, amorphous bi-catalytic catalysts of composition Ni59Nb40Pt1-xYx (Y=Cu, Ru, x=0.4% at.) have been developed, obtained by mechanical alloying, resulting in higher current densities and an improvement in tolerance to adsorbed CO vs. Ni59Nb40Pt1 catalyst. By using voltammetric techniques, the appearance of three oxidation peaks can be observed. The first peak could be associated with the electrooxidative process of ethanol/bioethanol to acetaldehyde, the second peak could be the oxidation of acetaldehyde to acetic acid, and the last peak might be the final oxidation to CO2. Chrono-amperometric experiments show qualitative poisoning of catalyt...
A novel heteropolyanion-based ionic hybrid was prepared by combining the divalent ionic liquid (IL) cation of 1,1'-(butane-1,4-diyl)-bis(3-methylimidazolium) with the Keggin-structured V-containing heteropolyanion, and characterized by ^1H NMR, FT-IR, ESI-MS, XRD, SEM, TG, BET surface area, melting point, and elemental analysis. Its catalytic activity was evaluated in the hydroxylation of benzene with aqueous H2O2, including the testing of the influence of organic cations, catalytic reusability and optimization of reaction conditions. This hybrid is characterized to be semi-amorphous nanoparticles with a IL-like composition. The hybrid catalyst leads to the liquid-solid biphasic reaction system for hydroxylation of benzene with H2O2, presenting such advantages as high catalytic activity, c...
Iron nanoparticles were produced using extracts of green tea leaves (GT-Fe NPs). The materials were characterized using TEM, SEM/EDX, XPS, XRD, and FTIR techniques and were shown to contain mainly iron oxide and iron oxohydroxide. The obtained nanoparticles were then utilized as a Fenton-like catalyst for decolorization of aqueous solutions containing methylene blue (MB) and methyl orange (MO) dyes. The related experiments investigated the removal kinetics and the effect of concentration for both MB and MO. The concentrations of dyes in aqueous solution were monitored using ultraviolet-visible (UV-vis) spectroscopy. The results indicated fast removal of the dyes with the kinetic data of MB following a second order removal rate, while those of MO were closer to a first order removal rate. T...
The author analyzes conference materials, emphasizing the studies and latest developments useful for industrial heterogeneous catalysis in view of the requirements of green chemistry. Industrial catalysts is developing along a nanometer scale, so especial attention is devoted to analyzing the reports in the Nanochemistry section on the creation of nanocatalysts, the production of active phase nanoparticles, and the formation of new synthesized material properties. The catalysts developed earlier by Russian research in cooperation with Belarusian scientists are considered, and it is shown that not only are expensive nanocontacts extremely promising for industry, but the efficient and economic low-percentage new generation of nanocatalysts synthesized by wet chemistry and containing nanopart...
Statistically based experimental designs were applied to screen and optimize the bioleaching of spent hydrocracking catalyst by Penicillium simplicissimum. Eleven factors were examined for their significance on bioleaching using a Plackett-Burman factorial design. Four significant variables (pulp density, sucrose, NaNO"3, and yeast extract concentrations) were selected for the optimization studies. The combined effect of these variables on metal bioleaching was studied using a central composite design (CCD). Second-order polynomials were established to identify the relationship between the recovery percent of the metals and the four significant variables. The optimal values of the variables for maximum metals bioleaching were as follows: pulp density (4.0%, w/v), sucrose (90g/L), NaNO"3 (2...
Catalytic activity of industrial metallic wastes in coal liquefaction was examined in a 100lb/day continuous coal processing development unit. Red mud, a waste material from the aluminium industry, and an electric furnace flue dust containing Ni, Mo, Co and Fe showed a pronounced effect on the conversion of a Kentucky bituminous coal. Coal conversion and oil production increased significantly with the addition of red mud and flue dust. Comparison of the catalytic activity of pyrite, red mud, and flue dust, based on selectivity analysis, showed that red mud was the most desirable disposable catalyst. However, if the primary goal of coal liquefaction is high oil production, irrespective of hydrogen consumption, pyrite is the most active catalyst among those discussed in the paper.
Cyclization of deproteinized natural rubber (DPNR) or purified natural rubber latex was effectively performed in latex phase by using trimethylsilyl-trifluoromethane sulfonate or trimethylsilyl triflate (TMSOTF) as a novel catalyst, which is still not reported in the case of natural rubber latex. Various cyclization conditions affecting the degree of cyclization were studied, such as dry rubber contents, temperature, TMSOTF concentrations, and time. The cyclized products were characterized by FTIR, Raman, 1H-, and 13C-NMR spectroscopies, as well as DSC and TGA. The degree of cyclization was estimated by 1H-NMR spectrum. It was found that the degree of cyclization in NR was a function of cyclization conditions. The thermal stability of cyclized DPNR increased with the degree of cyclization....
All of the direct reaction schemes described and the corresponding process schemes are still in an exploratory state. Ethylene by oxidative coupling of methane could become competitive if process schemes are developed with significantly less expenditures for separation of the product from unconverted feed. No encouragement for formaldehyde from methane can be presently derived from the existing knowledge. Liquid-phase oxidation of methane to methanol appears to be attractive but no final judgement is possible at present. Oxidative dehydrogenation of ethylene and propane look promising although further catalyst improvement is required. Acetic acid from ethane and acrylonitrile from propane have a certain potential as an alternative to present technology. The outlook for acrolein and acrylic acid from propane is less favourable; new concepts for catalyst design are necessary. (orig.)
Biomass gasification provides the potential to efficiently and economically produce a renewable source of a clean gaseous fuel suitable for power generation or synthesis gas (syngas) applications. An important side benefit of the use of biomass is the effective minimization of the primary greenhouse gas, carbon dioxide (CO{sub 2}), by providing a means to close-loop the CO{sub 2} cycle. However, high molecular weight hydrocarbon constituents (tar) in the product gas from gasification can complicate the downstream uses of the gas. This paper discusses both the development of a low cost, disposable catalyst system that can eliminate these heavy hydrocarbons from the gas and the use of the catalyst in conjunction with the Battelle high-throughput gasification process for power generation and synthesis applications. (author)
The cyclic voltammetry indicated that the oxygen reduction reaction (ORR) proceeded by the four-electron pathway mechanism on larger Ag particles (174 nm), and that the ORR proceeded by the four-electron pathway and the two-electron pathway mechanisms on finer Ag particles (4.1 nm), simultaneously. The kinetics towards ORR was measured at a rotating disk electrode (RDE) with Ag/C electrode. The number of exchanged electrons for the ORR was found to be close to four on larger Ag particles (174 nm) and close to three on finer Ag particles (4.1 nm). The zinc-air battery with Ag/C catalysts (25.9 nm) was fabricated and examined. (author)
The ammoxidation of propane over VSb{sub y}O{sub x} catalysts (y=1, 2, 5) was investigated with respect to the role of different oxygen species in the selective and non selective reaction steps using transient experiments in the Temporal Analysis of Products (TAP) reactor. Only lattice oxygen is involved in the oxidation reactions. Using isotopic labelled oxygen it is shown that two different active sites exist on the surface. On site A, which can be reoxidized faster by gas phase oxygen compared to site B, mainly CO is formed. On site B CO{sub 2} and acrolein as well as NO and N{sub 2}O in the presence of ammonia in the feed gas are formed and reoxidation mainly occurs with bulk lattice oxygen. (orig.)
The monoanionic bidentate Schiff base, N-(phenolyl)-benzaldimine (HL), has been employed to synthesize a new vanadium(IV) complex of general composition [VO(L)2] (where L = O, N donor of Schiff base). The ligand and complex have been fully characterized by elemental analyses, molar conductance data, FT-IR, 1H- and 13C-NMR, and UV-Vis spectroscopies. Oxidation of alcohols to their corresponding aldehydes and ketones was conducted by this complex catalyst using Oxone as oxidant under biphasic reaction conditions (CH2Cl2/H2O) and tetra-n-butylammonium bromide as phase transfer agent under air at room temperature.
A comparative study on the thermal and catalytic degradation of polybutylene terephthalate (PBT) at atmospheric pressure was conducted. The weight loss of PBT under thermal degradation was significantly influenced by the temperature between 360degreeC and 380degreeC, but little affected by the PBT particle size. Four groups of catalysts include metal chloride, metal oxide, metal acetate, and metal copper powder were used to test PBT degradation activity. Copper (II) chloride is the most active one for increasing the percentage PBT weight loss more than 100% in comparison with the result of thermal degradation at a temperature of 360degreeC for 30min. PBT and catalyst mixtures can be prepared by impregnation and physical method, the former resulted in a better PBT degradation. The percentag...
The program goals for the first quarter were to located and contact potential manufacturers of these components, evaluate their level of interest, and begin discussions of the type and design of the prototypes to be fabricated for their evaluation. Thoughtful discussion at this stage would result in fabricating prototypes which answer the greatest number of questions possible for a given manufacturer at the lowest cost to this program. In the present economy many manufacturing firms have almost no funds for testing and evaluating new materials. This places a greater burden on the data obtained from outside laboratories. In many cases this data will be used to make that first evaluation on MRCC`s (metal reinforced carbon composites) suitability for a given application and give firms the confidence to commit to a evaluation program. In Exhibit 1, which is attached to this report the authors have the first set of data from outside laboratories. This has been ...
The objectives of this project are to develop feasible synthetic routes to produce (1) 4(4`-hydroxy-5`,6`,7`,8`-tetrahydro-l`-naphthylmethyl )- 6-methyldibenzothiophene, and (2) a 1-hydroxynaphthalene-benzothiophene polymer. Our experimental work during this quarter concentrated on. As several possible synthetic routes to the target molecule, 4(4`-hydroxy-5`,6`,7`,8`-tetrahydro- l`-naphthylmethyl )-6-methyldibenzothiophene. We tried synthesizing the intermediates for our first method, in which we couple a metalated 4-methyldibenzothiophene with 4-formyl-5,6,7,8-tetrahydro-1-naphthol. We found that we could easily metalate dibenzothiophene, and then add a methyl group to the 4-position to give 4-methyldibenzothiophene in greater than 80% yield by using t-butyllithium in tetrahydropyran followed by dimethylsulfate. However, adding the second metal to the desired 4` position using the same method was more difficult, and instead the reaction occurred on the methyl ...
This supplement is published once a year as a complement to the Short- Term Energy Outlook, Quarterly Projections. The purpose of the Supplement is to review the accuracy of the forecasts published in the Outlook, make comparisons with other independent energy forecasts, and examine current energy topics that affect the forecasts. Chap. 2 analyzes the response of the US petroleum industry to the recent four Federal environmental rules on motor gasoline. Chap. 3 compares the EIA base or mid case energy projections for 1995 and 1996 (as published in the first quarter 1995 Outlook) with recent projections made by four other major forecasting groups. Chap. 4 evaluates the overall accuracy. Chap. 5 presents the methology used in the Short- Term Integrated Forecasting Model for oxygenate supply/demand balances. Chap. 6 reports theoretical and empirical results from a study of non-transportation energy demand by sector. The empirical analysis involves ...
Three test instruments are being evaluated to determine the feasibility of using photoacoustic technology for measuring unburned carbon in fly ash. The first test instrument is a single microwave frequency system previously constructed to measure photoacoustic signals in an off-line configuration. A second off-line instrument was constructed based in part on lessons learned with the first instrument, but which also expands the capabilities of the first instrument. Improvements include a control loop to allow more constant microwave power output and an ability to operate over a range of microwave frequencies. The third instrument, the on-line version of the fly ash monitor, has been designed, constructed, and initial efficiency tests have been conducted on the monitor's electrical components. This quarter focused on improving the signal strength of the accelerometer by increasing the power level of the microwaves that induced the thermo-elastic effect, and ...
Laser-assisted processing techniques, utilized to produce fine, metal grid patterns for high-efficiency solar cells, are being investigated, developed, and characterized. The work performed in the third quarter of this contract is detailed here. A preliminary economic evaluation has yielded the conclusion that laser-assisted pyrolysis of spun-on silver neodecanoate is the most promising of all the metallization techniques being investigated in this contract. Early adhesion problems have been solved by optimizing deposition parameters. Linewidth studies have been carried out as a function of laser power, scan speed, and film thickness. Preliminary solar cells have been fabricated and characterized using this metallization scheme. Silver neodecanoate films have also been decomposed using a pulsed uv laser and metal mask. A detailed study of the various models of localized surface temperature rise in silicon due to laser heating has been carried out. A review of this ...
Work on this coke oven gas cleaning demonstration project (CCT-II) this quarter has been focused on Phase IIB tasks, and include engineering, procurement, construction, and training. Additionally, plans for changes in the operating schedule of the coke plant that affect the demonstration project are described. Engineering efforts are nearly complete. Remaining to be finalized is an assessment of electrical heat tracing/insulation needs for pipe lines, assessment of fire protection requirements, and instrument modifications. Procurement of all major equipment items is complete, except for possible additions to fire fighting capabilities. Major focus is on expediting pipe and structural steel to the project site. Civil construction is complete except for minor pads and bases as required for pipe supports, etc. Erection of the hydrogen sulfide and ammonia scrubber vessels is complete. Installation of scrubber vessel internals is underway. A subcontractor has been ...
An advanced process for the separation of hydrogen sulfide (H{sub 2}S) from coal gasification product streams through an electrochemical membrane is being developed. H{sub 2}S is removed from the syn-gas stream, split into hydrogen, which enriches the exiting syn-gas, and sulfur, which is condensed from an inert sweep gas stream. The process allows removal of H{sub 2}S without cooling the gas stream and with negligible pressure loss through the separator. The process is made economically attractive by the lack of need for a Claus process for sulfur recovery. Membrane manufacturing coupled with full-cell experimentation was the primary focus this quarter. A tape-casted zirconia membrane was developed and utilized in one full-cell experiment (run 25); run 24 utilized a fabricated membrane purchased from Zircar Corporation. Results are discussed.
This report is to present the progress made on the project ''Establishment of an Environmental Control Technology Laboratory (ECTL) with a Circulating Fluidized-Bed Combustion (CFBC) System'' during the period January 1, 2005 through March 31, 2005. The following tasks have been completed. First, the renovation of the new Combustion Laboratory is nearly complete, and the construction of the Circulating Fluidized-Bed (CFB) Combustor Building is in the final stages. Second, the fabrication and manufacture of the CFBC Facility is being discussed with a potential contractor. Discussions with potential contactor regarding the availability of materials and current machining capabilities have resulted in the modification of the original designs. The selection of the fabrication contractor for the CFBC Facility is expected during the next quarter. Third, co-firing experiments conducted with coal and chicken waste have been initiated in ...
North Slope of Alaska has huge oil deposits in heavy oil reservoirs such as Ugnu, West Sak and Shrader Bluff etc. The viscosity of the last two reservoir oils vary from {approx}30 cp to {approx}3000 cp and the amount in the range of 10-20 billion barrels. High oil viscosity and low formation strength impose problems to high recovery and well productivity. Water-alternate-gas injection processes can be effective for the lower viscosity end of these deposits in West Sak and Shrader Bluff. Several gas streams are available in the North Slope containing NGL and CO{sub 2} (a greenhouse gas). The goal of this research is to develop tools to find optimum solvent, injection schedule and well-architecture for a WAG process in North Slope shallow sand viscous oil reservoirs. In the last quarter, we have developed streamline generation and convection subroutines for miscible gas injection. The WAG injection algorithms are being developed. We formulated a four-phase relative ...
DOE's program for the conversion of coal to liquid fuels was begun by two of DOE's predecessor agencies: Office of Coal Research (OCR) in 1962, and Bureau of Mines, US Department of the Interior, in the 1930's. Current work is aimed at improved process configurations for both catalytic and non-catalytic processes to provide more attractive processing economics and lower capital investment. The advantage of coal liquefaction is that the entire range of liquid products, especially boiler fuel, distillate fuel oil, and gasoline, can be produced from coal by varying the type of process and operating conditions used in the process. Furthermore, coal-derived liquids have the potential for use as chemical feedstocks. To provide efficient and practical means of utilizing coal resources, DOE is supporting the development of several conversion processes that are currently in the pilot plant stage. DOE, together with the Electric Power Research Institue, has contracted ...
The objectives of this project are to support the DOE direct coal liquefaction process development program and to improve the useful application of analytical chemistry to direct coal liquefaction process development. Independent analyses by well-established methods will be obtained of samples produced in direct coal liquefaction processes under evaluation by DOE. Additionally, analytical instruments and techniques which are currently underutilized for the purpose of examining coal-derived samples will be evaluated. The data obtained from this study will be used to help guide current process development and to develop an improved data base on coal and coal liquids properties. A sample bank will be established and maintained for use in this project and will be available for use by other researchers. The reactivity of the non-distillable resids toward hydrocracking at liquefaction conditions (i.e., resid reactivity) will be examined. From the literature and data experimentally obtained, ...
The purpose of this study is to extend the knowledge base for wetland treatment to include processes and substances of particular importance to small, on-site systems receiving oil and gas well waste water. Collection of data on the sorption of heavy metals and the degradation of toxic organics is one of the key tasks. The toxic organics phenolics and anthracene, and chromium and copper have been selected as target adsorbates. An information search was performed on oil refinery waste treatment wetland systems.
The objectives of the Upgraded Coal Interest Group (UCIG) are as follows: Review and update the status of various coal upgrading technologies and developments and critically assess the results. Perform engineering screening analyses on various coal upgrading approaches. Perform commercialization analyses that will promote the availability and use of upgraded coal products by quantifying the benefits of using them. Identify market opportunities for introduction of upgraded coals. Perform critical analyses on a variety of coals and technologies in areas important to users but not readily available. Perform critical experiments which will show the differences between technologies.
Purpose - The purpose of this research is to investigate the influence of psychological contracts on the adjustment and organisational commitment of expatriates during international business assignments. The study also aims to investigate the influence of psychological barriers to expatriate adjustment. Design/methodology/approach - A unique survey questionnaire was developed to collect data from 219 Taiwanese business expatriates during the first quarter of 2007. A LISREL analysis is used to test the hypotheses of the research framework. Findings - The study finds that: perceived fulfilment of the psychological contracts of expatriates significantly influences both their adjustment to foreign situations and their organisational commitment; psychological barriers to adjustment have a negat...
To expand the information base on molecular accessibility in solvent swelled coal, Argonne Premium Coal Samples (APCS) were swelled in polar, basic solvents before and after moisture loss and upon air oxidation. So far studies have been reported on the changes in pore size distribution as a function of temperature when polar basic swelling solvents are used. Additional studies employing EPR spin probe techniques performed on the breaking up of the hydrogen bonding between bedding planes were later confirmed by magnetic resonance imaging at Argonne National Lab and the University of Illinois.
A finite three-dimensional layer-by-layer photonic crystal with planar defects in a layer is shown to drastically modify the spontaneous emission rate of an embedded dipole. Finite-difference time-domain calculations with one quarter symmetric boundary condition and perfectly matched layer demonstrate the strong enhancement effects induced by the cavity resonance of defect modes and band-edge resonant modes. Simulation shows that the emission spectra are quite different when the position or polarization of the dipole is changed. Moreover, the extraction efficiency is calculated to observe the percentage of light leakage through a substrate.
Laser-assisted processing techniques for producing high-quality solar cell metallization patterns are investigated, developed, and characterized. The tasks comprising these investigations are outlined. A new batch of solar cells was processed using the laser decomposition of spun-on silver neodecanoate to metallize cells. Decomposition of silver neodecanoate was carried out at different laser powers on different cells on a given wafer to determine whether this would have any effect on cell performance. Solar cells which were written with laser powers of 5 to 8 watts, gave excellent results with cell efficiencies in the range of 14 to 16%.
A new lens was installed in the laser; the laser power was lowered and solar cells were made at different power levels. The concentration of the silver neodecanoate solution was changed to reduce linewidth. A cell fabrication run was completed using low-resistivity float-zone silicon. Experiments were initiated to investigate the use of titanium organometallic film, which not only forms an AR coating with a 400/sup 0/C hard bake, but may also help in bypassing front-metal evaporation because of high-reactivity of Ti with silicon. Progress in these areas is discussed.
... These highly energy efficient panels of organic luminescence are far removed from the bulbs and filaments of current lighting technology. 28-04-11 Source : Star Projects Results: 1-10 of 251 Page(s) 1 of 26 Next Limit search to articles published within the last Month Quarter Year No limit Follow us on Facebook Share an article You can share any article via social networking sites or email it to friends. Click the SHARE icon, select from the list that appears, and the article ...
The purposed project is a commercial-scale ethanol-fuel facility with a capacity of twenty million gallons per year of fuel-grade ethanol. In addition, 70,000 tons per year of distillers dried grains will be produced. The following tasks and issues are addressed: process engineering - process descriptions, plant layout, and design; economics and finance - overview of capital and operating costs; environmental analysis - preliminary project description; and permit processing and legal issues. (MHR)
This paper deals with dynamical behavior of a nonlinear suspension system. We examine chaotic motion in a vehicle suspension system with hysteretic nonlinearity excited by a road profile. A one degree of freedom quarter-car model with nonsymmetric potential is investigated. The Melnikov criterion is used to study the intersection of stable and unstable manifolds and transition to chaos for the system. The condition for chaotic vibration is found using a Melnikov function. Chaotic motion also is indicated by a bifurcation diagram and Lyapunov exponents.
In this first quarterly technical report for DOE Contract No. DE-AC22-87PC79654, a description of the background, technology, and application is provided. The design and fabrication of advanced combustion chambers were completed during this period. Initial testing on both the bare metal and refractory lined advanced chambers were initiated. The units were tested initially with gas but primarily with coal. A Pittsburgh No. 8 pulverized coal was used for these test activities. Both advanced chambers pulsed well.
Evaluation of ageable beta alloys Ti-17V-2Fe-2Co-3Al, Ti-17V-7.5Co-3A1 and Ti-8Mo-8V-5Co-3Al continued with room and elevated temperature smooth and notched tensile tests, creep stability, oxidation and stress-corrosion tests. Ti-17V-7.5Co-3Al aged more r...
Consol R&D is conducting a three-year program to characterize process and product streams from direct coal liquefaction process development projects. The program objectives are two-field: (1) to obtain and provide appropriate samples of coal liquids for the evaluation of analytical methodology, and (2) to support ongoing DOE-sponsored coal liquefaction process development efforts. The two broad objectives have considerable overlap and together serve to provide a bridge between process development and analytical chemistry.
Consol R&D is conducting a three-year program to characterize process and product streams from direct coal liquefaction process development projects. The program objectives are two-fold: (1) to obtain and provide appropriate samples of coal liquids for the evaluation of analytical methodology, and (2) to support ongoing DOE-sponsored coal liquefaction process development efforts. The two broad objectives have considerable overlap and together serve to provide a bridge between process development and analytical chemistry.
This paper is a quarterly report describing the use of a new soil gas collection device which allows the collection of soil gas in the field for later analysis in the laboratory. It describes the installation of this sampling device and the procedure for setting the probe, extraction of soil gas beneath the surface, and sealing of the soil gas for transport. The sites used for initial testing was the top of Yucca Mountain and Crystal Spring in Ash Meadows National Wildlife Refuge. The results from this initial test showed no volatile matter present in the soil at these locations.
The Meteorology and Air Quality (MAQ) group at Los Alamos National Laboratory maintains and operates a large network of environmental air samplers called AIRNET. Some of these samplers are located near Material Disposal Area C at TA-50, a low-level radioactive waste burial site in the semiarid environment of the Pajarito Plateau, near Los Alamos. AIRNET sampling media consist of a filter and silica gel. They are exchanged once every 2 weeks. Presented are 5 months of air sampling results for 5 stations operating in the vicinity of Material Disposal Area C.
Short-term radon measurements were used to make a comparison between weekly screening tests and seasonal concentration. The screening measurements were made in an indoor environment over a period of one quarter during early summer and the results are compared with the measured average radon level over that period. In these experiments, the envelope-type and plastic bag monitors were used for screening and long term radon concentration measurements, respectively. The results show that one cannot achieve predicting the seasonal mean radon concentration based on weekly measurements better than 50% under the conditions reported. (author).
Short-term radon measurements were used to make a comparison between weekly screening tests and seasonal concentration. The screening measurements were made in an indoor environment over a period of one quarter during early summer and the results are compared with the measured average radon level over that period. In these experiments, the envelope-type and plastic bag monitors were used for screening and long term radon concentration measurements, respectively. The results show that one cannot achieve predicting the seasonal mean radon concentration based on weekly measurements better than 50% under the conditions reported. (author).
We consider the alternating sign matrices of the odd order that have some kind of central symmetry. Namely, we deal with matrices invariant under the half-turn, quarter-turn and flips in both diagonals. In all these cases, there are two natural structures in the centre of the matrix. For example, for the matrices invariant under the half-turn the central element is equal $\\pm 1$. It was recently found that $A^+_{HT}(2m+1)/A^-_{HT}(2m+1)$=(m+1)/m. We conjecture that similar very simple relations are valid in the two remaining cases.
A High Performance Power System (HIPPS) is being developed. This system is a coal-fired, combined cycle plant with indirect heating of gas turbine air. Foster Wheeler Development Corporation and a team consisting of Foster Wheeler Energy Corporation, Bechtel Corporation, University of Tennessee Space Institute and Westinghouse Electric Corporation are developing this system. In Phase 1 of the project, a conceptual design of a commercial plant was developed. Technical and economic analyses indicated that the plant would meet the goals of the project which include a 47 percent efficiency (HHV) and a 10 percent lower cost of electricity than an equivalent size PC plant. The concept uses a pyrolysis process to convert coal into fuel gas and char. The char is fired in a High Temperature Advanced Furnace (HITAF). The HITAF is a pulverized fuel-fired boiler/air heater where steam is generated and gas turbine air is indirectly heated. The fuel gas generated in the pyrolyzer is then used to ...
Only 15mol% of l-proline in ethanol proved to be a very efficient catalyst for the one-pot synthesis of a wide variety of highly substituted pyridines at room temperature. The methodology is mild, efficient, high yielding, and the products can be directly recrystallized from hot ethanol.
This report presents the operating results for Run 244 at the Advanced Coal Liquefaction R and D Facility in Wilsonville, Alabama. This run was made in an all-distillate Integrated Two-Stage Liquefaction (ITSL) mode using Illinois 6 coal from the Burning Star mine. The primary objective was to demonstrate the effects of temperature programming an aged catalyst batch on the ITSL product slate, especially on the net C/sub 1/-C/sub 5/ gas production and hydrogen consumption. Other objectives were to demonstrate the effect of fresh catalyst addition and to age the catalyst batch for an extended run with catalyst addition and withdrawal. Run 244 began on 4 July 1983 and continued through 27 September 1983. During this period, 182.9 tons of coal was fed in 1872 hours of operation. Seven special product workup material balances and two hydrotreater balances were defined, and the results are presented herein. ...
The diffusion of alkali vapours in the anode compartment of a DIR-MCFC produces the deactivation of the internal reforming catalyst. Sets of ceramic porous membranes purposed to limit the diffusion have been manufactured by different techniques and the influence of the preparation technique and of the preparative variables on the morphological characteristics of the membranes structures has been studied.
Details are given of the Sasol operation in South Africa. Flow sheets are provided for Sasol 1 and Sasol 2 and 3. The Sasol 1 plant produces waxes, liquid fuels, pipeline gas and chemicals; the Sasol 2 and 3 plants primarily produce ethylene, gasoline and diesel fuel. The versatility of the process is emphasized. The product selectivities of the fixed bed and Synthol reactors are shown and the properties of the products are compared. The influence of the catalyst on selectivity is examined.
The present results indicate that maximum selectivity to acrylic acid can be reached over V-P-Zr-O catalysts. When the hydrocarbon concentration is 5.1 vol.% the selectivity is about 30% at quite high paraffin conversion. Conclusively, some explanations to the observed facts can be given. The V-P-O catalyst promotion with lanthanum by means of mechanochemical treatment is distinguished by the additive uniform spreading all over the matrix surface. Such twophase system is highly active in propane conversion (lanthanum oxide) and further oxidation of the desired products. The similar properties are attributed to V-P-Bi-La-O catalyst. Bismuth, tellurium and zirconium additives having clearly defined acidic properties provoke the surface acidity strengthening and make easier desorption of the acidic product (acrylic acid) from the surface lowering its further oxidation. Additionally, since bismuth and zirconium are able to form ...
It is demonstrated that highly dispersed molybdenum sulfide catalysts are prepared by using Mo(CO){sub 6} adsorbed on the support. The structure of ultradispersed molybdenum sulfide is suggested by EXAFS techniques to be different from that of MoS{sub 2}. The TOF of the thiophene HDS is almost invariant with the dispersion of molybdenum sulfide at a high molybdenum dispersion, whereas the TOF of the hydrogenation greatly increases with increasing dispersion. On the basis of the HDS activity and optimum Co/Mo ratio of Co-Mo/Al{sub 2}O{sub 3} catalysts having a variety of molybdenum dispersion fabricated by using carbonyl complexes, it is demonstrated that highly active HDS catalysts are prepared by highly dispersing molybdenum sulfide phases. Edge decorations of molybdenum sulfides by cobalt are suggested for the synergy generation between cobalt and molybdenum sulfides. (orig.) [Deutsch] Unter Verwendung von auf dem Traeger ...
Structural units of a hydrogen fuel cell whose characteristics are advisable to investigate by different neutron scattering methods are discussed. The results obtained with the use of Bragg diffraction and small-angle neutron scattering from fuel membranes, nanocarbon-platinum catalysts, and Zn_1_-_xCu_xO hydrogen storage systems are presented.
The investigations of lignite hydroliquefaction were aimed at improving reaction control in order to minimize residue and gas portion and hence increase the oil yield. To reach this goal, the process parameters were optimized and various catalysts tested for use in sump phase hydrogenation. Detailed investigations were also carried out on the problem of calcium carbonate agglomeration and the maceral decomposition behaviour of different lignite samples under hydrogenation conditions.
Single and binary metal molybdates, supported on silica (80 wt% active phase/20 wt% SiO{sub 2}), having the formula AMoO{sub 4}, where A = Ni, Co, Mg, Mn, and/or Zn, and some ternary molybdates having the formula Ni{sub 0.45}Co{sub 0.45}X{sub 0.066}MoO{sub 4}, where X = P, Bi, Fe, Cr, V, and Ce, were investigated for the oxydehydrogenation of propane to propylene. The reaction is catalytic and is first order in propane disappearance, consistent with the abstraction of a methylene hydrogen being the rate limiting step. Propane conversion and yields of propylene produced vary greatly with the choice of the A metal of the molybdate and the surface area of the catalyst. At 560{degrees}C and atmospheric pressure, the highest propane conversion and highest propylene yields are obtained with NiMoO{sub 4}/SiO{sub 2} (16% at 27% conversion), closely followed by Ni{sub 0.5}Co{sub 0.5}MoO{sub 4}/SiO{sub 2}. The molybdenum content of the compositions greatly influences the ...
Preparation and electrocatalytic reactions of nano porous materials in biodegradable fluids were studied. Electrochemical etching was conducted to selectively extract metallic elements from alloys to form porous structures. Electrocatalytic properties of the porous electrodes were characterized. Comparative studies on the electrochemical activities of the nano porous metallic electrodes with bulk metallic wire catalysts were performed. It is found that the current density at the nano porous electrode is three times higher than that of the bulk electrode
This report forms part of a joint study on a PEFC propulsion system for surface ships, summarized in a presentation to this Seminar, entitled {open_quotes}Study on a Polymer Electrolyte Fuel Cell (PEFC) Propulsion System for Surface Ships{close_quotes}, and which envisages application to a 1,500 DWT cargo vessel. The aspect treated here concerns an experiment in reducing by methanation to a level below 10 ppm the CO that is contained to around 1% in reformate gas.
A general palladium-catalyzed carbonylative Sonogashira coupling of benzyl chlorides with terminal acetylenes has been established. Depending on the alkyne 1,4-diaryl-3-butyn-2-ones or substituted furanones are obtained in moderate to good yields. Best catalytic performance is achieved applying a mixed Pd(PPh(3))Cl(2)/P(OPh)(3) catalyst system. PMID:21968528
The catalytic dehydration of methanol to dimethyl ether was investigated for application on-board a methanol fuelled vehicle. Several catalysts have been tested in a fixed bed reactor. Our approach is to develop a small and efficient reactor converting liquid MeOH under pressure and at low reaction temperatures. (author) 2 figs., 5 refs.
Nanocrystalline processing by inert gas condensation has the inherent advantages of generating: (1) high surface area nanoclusters, (2) non-stoichiometric oxides, and (3) high dispersions of dopants. This approach is exploited in the synthesis of fluorite-structured catalysts for SO{sub 2} reduction by CO. Nanocrystalline CeO{sub 2{minus}x}, La-doped CeO{sub 2{minus}x}, and Cu-doped CeO{sub 2{minus}x} were produced by magnetron sputtering from a pure or mixed metal target, followed by controlled oxidation of the metallic clusters. The as-prepared doped and undoped nanocrystalline CeO{sub 2{minus}x} materials were found to be excellent catalysts for complete SO{sub 2} conversion to elemental sulfur. Undoped nanocrystalline CeO{sub 2{minus}x} enabled light-off at 460 C, a temperature {approximately} 120 C lower than that over polycrystalline CeO{sub 2}, which is a novel effective catalyst itself. The high catalytic activity ...
The catalytic performance of alkaline-treated zeolite H-ZSM-5 in the conversion of methanol to gasoline has been studied. After treatment with 0.20M NaOH, the total conversion capacity increased by a factor of 3.3, and the selectivity towards the gasoline fraction increased by a factor of 1.7. Physical characterization indicated the formation of mesopores and improved crystallinity.
The kinetics of the reaction of carbon dioxide in MDEA solutions were studied both experimentally and theoretically. It is concluded that MDEA acts as a homogeneous catalyst for CO/sub 2/ hydrolysis, and as a result the rate of absorption in aqueous MDEA solutions is significantly larger than one would calculate by simply taking into account the alkalinity of the reaction. A possible zwitterion mechanism is proposed for this reaction. The minor effect of ionic strength were also studied with the presence of other ions. 19 references, 6 figures.
Details of a series of reactions for the production of ethylene glycol using a catalyst of Nafion solid perfluorosulfonic acid resin was detailed. The reactions included the carbonylation of formaldehyde and esterification and then hydrogenation of the product of the carbonylation, glycolic acid. Other preparations included in the work included methyl glycolate, acetylglycolic acid, methyl acetylglycolate, and methyl methoxyacetate.
DescriptionEnzymes are natural catalysts that are used increasingly to replace environmentally harmful chemicals and to achieve better catalytic selectivity during pulp and paper processing. The main objective of this project is to identify novel plant enzymes for deeper understanding of the process of fibre formation and for future improvement of the quality parameters of wood fibres. Specific modification of the fibre characteristics will facilitate their use as raw materials for the current pulp and pap [continued...
This paper reports the effectiveness of solvents on the liquefaction of 11 different Turkish lignites investigated by using tetralin, creosote, and anthracene oils. The highest total conversions were obtained with tetralin. The catalytic effects of CoMo and red mud were compared by using creosote oil as the solvent. It was found that red mud catalyzed mainly the asphaltene formation reaction for the given experimental conditions. The additional of CoMo significantly catalyzed the liquefaction reaction, thus increasing the lignite conversion and oil formation.
Processes for the hydrogenation of carbon monoxide have had commercial importance since about 1920, when the commercial production of methanol and higher alcohols on oxide catalysts began. Soon thereafter Fischer and Tropsch discovered that liquid hydrocarbons could be synthesized from carbon monoxide and hydrogen over Group VIII metal catalysts. Following extensive catalyst and process development efforts, this technology provided Germany with a source of liquid fuels during World War II. The period following the war saw an acceleration in research and development on the Fischer-Tropsch process, but the only commercial application that was to emerge was the SASOL process in the Union of South Africa. The oil crises of the 1970s have rekindled worldwide interest in indirect liquefaction technologies for the production of clean, high-quality motor fuels from coal. The development of more efficient coal gasification processes ...
Some applications of magnetic resonance in coal liquefaction research described briefly are: (1) investigation of the nature of carbon deposits on used coal-liquefaction catalysts, (2) determination of the fate of hydrogen during coal liquefaction, and (3) observation of transient free radicals during coal pyrolysis. The first two applications make use of cross-polarization /sup 13/C magnetic resonance combined with magic angle spinning, and the third application is an electron spin resonance study. (BLM)
Progress reports are presented for the following two areas: catalytic cracking studies with water-wet silica-alumina catalysts; and Fischer-Tropsch reactor studies where similarities and differences between fixed bed and slurry type reactors are investigated and further experiments conducted to measure mass transfer coefficients and reaction kinetics which are to be used in a model slurry reactor. The following are some of the conclusions. (1) The premise that the presence of liquid water might increase catalytic cracking activity was found to be invalid. It was demonstrated that cracking can occur at previously unobserved low temperatures (though at low conversions) and that an anomaly exists in that one of the catalysts tested shows an entirely different cracking behavior and probably follows a different cracking mechanism. (2) the diameter of a fixed-bed Fischer-Tropsch reactor critically affected the resistance of the reactor to plugging ...
The catalytic activities of various iron ores were investigated in the search for a high-activity catalyst for direct coal liquefaction. Laterite ores were shown to have a high catalytic activity in this process. Comparison of the ore with red mud in hydrocracking of 1-methylnaphthalene showed that the ore had higher activity in the hydrogenation of aromatic rings and in hydrocracking of alkylaromatics.
Most chemical reactions in industry and biology are catalytic and play a role at some stage of the processing of about 80% of the goods manufactured in the U.S., yet catalysis is a neglected subject in chemical education. This book integrates the fragmentary treatment accorded the topic until now. It covers, in a unified way, catalysis in solutions, by enzymes, in synthetic polymers within the molecular scale cages of zeolites and other molecular sieves, and on surfaces of inorganic solids. The central ideas are chemical; and principles are illustrated by emphasizing industrial reactions and catalysts.
... However blaming vitamin supplements on deaths, or mortality is silly, as the studies are not exactly kosher. Vitamin C in 2,000mg is good for allergies, and niacin (b3) in 10,0000mg is good for depression. This is all examples on how vitamin supplements can help. I call it a security blanket, as food these days is not so good due vitamin and mineral damage due to light, or storage. By the time we eat the apple from the supermarket, there is minimal vitamin and ...
A process is provided for conducting organic compound conversion over a catalyst composition comprising a supported crystalline zeolite having a high initial silica-to-alumina mole ratio, said supported zeolite being prepared by compositing said crystalline zeolite with alumina, reacting the composite with a particular hydrogen fluoride solution in a specified way, drying the hydrogen fluoride reacted composite, treating the dried composite by hydrolysis, ammonolysis and/or by contact with an ammonium salt solution, and calcining the resulting material.
The catalytic liquefaction of a Chinese bituminous coal was simulated by artificial neural network. Three liquefaction variables, catalyst loading, reaction temperature and reaction time were used as inputs and tetrohydrofuran (THF) conversion and toluene (T) conversion were used as outputs. The artificial neural network, trained by the experimental data, could represent the liquefaction process, with a mean squared deviation of less than 0.025. 7 refs.,1 fig., 3 tabs.
For the first time in scientific literature, in our joint work with Dr. G. Ladwig in 1978 it was established phase portraite of the oxide vanadium-phosphorus system within wide range of P/V ratios from 0.5 to 3.2. Some later those data were confirmed. By investigation of the properties of individual vanadium-phosphorus phases it was also shown that the active component of such catalysts in n-butane oxidation was vanadyl pyrophosphate phase (VO){sub 2}Pr{sub 2}O{sub 7}. From then the conclusion has been evidenced by numerous publications and at present it has been out of doubt practically all over the world. It was hypothized that the unique properties of (VO){sub 2}P{sub 2}O{sub 7} in the reaction of n-butane oxidation could be explained by the presence of paired vanadyl groups and nearness of the distances between neighbouring vanadyl pairs and that between the first and fourth carbon atoms in n-butane molecule. The molecule activation occured at the latter atoms ...
In this work, wet ball milling method is used in order to improve hydrogen sorption behaviour due to its improved microstructure of solid hydrogen materials. Compared to traditional ball milling method, wet ball milling has benefits on improvement of MgH{sub 2} microstructure and further influences on its hydrogen sorption behavior. With the help of solvent tetrahydrofuran (THF), wet ball milled MgH{sub 2} powder has much smaller particle size and its specific surface area is 7 times as large as that of dry ball milled MgH{sub 2} powder. Although after ball milling the grain size is decreased a lot compared to as-received MgH{sub 2} powder, the grain size of wet ball milled MgH{sub 2} powder is larger than that of dry ball milled MgH{sub 2} powder due to the lubricant effect of solvent THF during wet ball milling. The improved particle size and specific surface area of wet ball milled MgH{sub 2} powder is found to be determining its hydrogen sorption kinetics especially at relatively ...
This was a university-based research project in support of distributed reforming production technologies for hydrogen. Our objective was to examine the steam reforming of bio-ethanol and other related bio-derived liquids over non-precious metal catalyst systems to enable small-scale distributed hydrogen production technologies from renewable sources. The study targeted development of a catalytic system that does not rely on precious metals and that can be active in the 350-550 C temperature range, with high selectivity and high stability. To this end, we adopted a multi-prong research strategy, that included catalyst formulation and synthesis, detailed catalyst characterization, reaction kinetics and reaction engineering, molecular modeling and economic analysis studies. Our approach was an iterative one, where the knowledge gained in one aspect of the study was utilized to modify and fine-tune catalyst ...
The `Procurement Quality Function` is an element of the Body of Knowledge of Quality Engineering, as defined by the American Society for Quality Control (ASQC). This paper describes the Procurement Quality function which has been installed as an integral part of the Quality Engineering group of the Technical and Management Support Services (T&MSS) contractor to the United States Department of Energy (DOE) Yucca Mountain Site Characterization Project. Each of the elements of the T&MSS Procurement Quality Engineering (PQE) system is discussed along with the measurements obtained. With the installation and development of the PQE system we have attained more meaningful evaluation of supplier capability, reduction of procurement document review reject ratios from 31% to less than 2% per quarter, more effective measurement and control of supplier performance, and the ability to enter into a meaningful teaming effort with T&MSS suppliers.
In the field of international human resource management, studies have seldom examined organizational justice, social exchange, and psychological contract together as important factors in influencing the expatriate adjustment process. The purpose of this research is to fill the research gap by examining these factors and their relationships with expatriate adjustment. The researcher conducted a survey of Taiwanese business expatriates during the first quarter of 2007, collecting 219 valid samples for analysis. A hierarchical regression model was used to test the research framework hypotheses, which showed that expatriates' perception of organizational justice has a positive influence both on their perceptions of social exchange and on their psychological contract fulfillment. Expatriates' p...
The KENTORT II process includes integral fluidized bed zones for pyrolysis, gasification, and combustion of the oil shale. The purpose of this program is to design and test the KENTORT II process at the 50-lb/hr scale. Along with the major activity of assembling the components of the 50-lb/hr retort, work was also completed in other areas this quarter. Basic studies of the cracking and coking kinetics of model compounds in a fixed bed reactor were continued. Additionally, as part of the effort to investigate niche market applications for KENTORT II-derived products, a study of the synthesis of carbon fibers from the heavy fraction of KENTORT II shale oil was initiated.
The main goal of this research is to delineate the wetting behavior of coal and it subsequent effects on fine coal processing. As both bulk and surface properties of coal are interrelated and have a controlling role on the performance of these processes, a detailed study has been undertaken to correlate their influence on both wetting behavior and the response of coal to flotation and other unit operations encountered in fine coal processing. During the last quarter, the effect of coal rank on water retention capacity was investigated. The effect of pH on the vacuum flotation yield and the effect of desliming on the film flotation response of coal were also studied. 6 refs., 5 figs.
The Low Power and Shutdown (LPSD) PRA (Probabilistic Risk Assessment) Standard (ANS-58.22) is currently being drafted by a Writing Group under the auspices of the Risk Informed Standards Committee of the American Nuclear Society (ANS). The Writing Group includes representatives from nuclear utilities, US Nuclear Regulatory Commission (NRC), national laboratories, universities, and consultants with substantial experience producing LPSD PRAs. This draft standard is scheduled to be released for public comment in the second quarter of 2004, with publication by the end of 2004. The LPSD PRA Standard is based on a mature technology that shares many requirements with full power PRAs. It will provide specific methods and criteria whereby PRAs of appropriate quality and scope can be used in the conduct of plant decision-making and other activities, including addressing NRC requirements. This paper presents the current status of this standard.
In this paper Particle Bed Reactor (PBR) designs are discussed which use /sup 233/U and /sup 242m/Am as fissile materials. A constant total power of 100MW is assumed for all reactors in this study. Three broad aspects of these reactors is discussed. First, possible reactor designs are developed, second physics calculations are outlined and discussed and third mass estimates of the various candidates reactors are made. It is concluded that reactors with a specific mass of 1 kg/MW can be envisioned of /sup 233/U is used and approximately a quarter of this value can be achieved if /sup 242m/Am is used. If this power level is increased by increasing the power density lower specific mass values are achievable. The limit will be determined by uncertainties in the thermal-hydraulic analysis. 5 refs., 5 figs., 6 tabs.
The first year of this effort was focussed on the following broad objectives: (1) Analyze the molecular types present in shale oil (as a function of molecular weight distribution); (2) Determine the behavior of these molecular types in liquid-liquid extraction; (3) Develop the analytical tools needed to systematize the process development; (4) Survey the markets to assure that these have high value uses for the types found in shale oil; (5) Explore selective process means for extracting/converting shale oil components into concentrates of potentially marketable components; (6) Compile overview of the venture development strategy and begin implementation of that strategy. Each of these tasks has been completed in sufficient detail that we can now focus on filling in the knowledge gaps evident from the overview.
Based on the quarterly data from four open economies (the US, the UK, Canada, and Italy) and estimated correlations and impulse responses within the traditional vector autoregressive (VAR) analysis, we find that inflation, both in the short and long term, negatively affects consumption and investment, and has a positive influence on the current account. We propose an infinite-horizon optimizing model of an open economy with a fixed rate of time preference that explains these empirics. In this type of economy, households consume both durable and non-durable goods, firms operate under costly investment, and all the transactions involving consumption and investment are subject to cash-in-advance (CIA) constraints. Employing the new ?sign restriction? identification procedure due to Uhlig (J M...
This report provides a brief summary of the milestone for Quarter 1 of 2006 of the NATional CARBon Sequestration Database and Geographic Information System (NATCARB) This milestone assigns consistent symbology to the ''National CO{sub 2} Facilities'' GIS layer on the NATCARB website. As a default, CO{sub 2} sources provided by the Regional Carbon Sequestration Partnerships and the National Group are now all one symbol type. In addition for sinks such as oil and gas fields where data is drawn from multiple partnerships, the symbology is given a single color. All these modifications are accomplished as the layer is passed through the national portal (www.natcarb.org). This documentation is sent to National Energy Technology Laboratory (NETL) as a Topical Report and will be included in the next Annual Report.
A proposed metallization system for large area silicon solar cells with shallow junctions is outlined, and its desirable features are discussed. A baseline process sequence for the nickel palladium metallization system (NPMS) is delineated. This baseline process sequence is serving as the starting point from which process variations are being performed. The eventual goal is optimization of the NPMS process and determination of the control ranges for NPMS process variables. Initial studies of palladium displacement and electroless chemical plating solutions used in the baseline NPMS have begun and progress is reported. In support of this work, an annotated bibliography (45 citations) dealing primarily with palladium plating and palladium-silicon contact formation has been prepared (and will be subject to updating in the future reports).
Shell UK Exploration and Production, operating in the North Sea on behalf of Shell UK and Esso UK is presented developing the Teal and Guillemot fields in the Central North Sea (CNS). As part of this development it contracted with Single Buoy Moorings Inc., (SBM) for the design, supply and installation of a newbuilt floating Production Storage and Offloading (FPSO) vessel. The work is executed in close cooperation between Shell Expro (Client) and SBM (Contractor) and its main sub contractors. The system is due to be installed during the third quarter of 1996. After a short description of the field development and the FPSO vessel this paper outlines the contractual arrangements and the organization set-up to perform the work. A summary of the lessons learned (by SBM) is given. The opinions expressed in this paper are entirely that of the author and may not necessarily reflect the opinion of other parties involved in the CNS FPU project.
The major goal of this contract is to define fine grid lines using laser-assisted metallization and to demonstrate the fabrication of high-efficiency cells using this process. During this period a solar cell run was completed using low-resistivity float-zone silicon. Grid lines were written by spinning silver neodecanoate solution after the Ti-Pd evaporation. This run produced cell efficiencies as high as 11.2% prior to antireflection coating and 16.6% after the AR coating. Open-circuit voltage was approx.604 mV and short-circuit current density was approx.35 mA/cmS.
The purpose of this project is to demonstrate targeted infill and extension drilling opportunities, better determinations of oil-in-place, methods for improved completion efficiency and the suitability of waterflooding in certain shallow-shelf carbonate reservoirs in the Williston Basin, Montana, North Dakota and South Dakota. Improved reservoir characterization utilizing 3-dimensional and multi-component seismic area is being investigated for identification of structural and stratigraphic reservoir compartments. These seismic characterization tools are integrated with geological and engineering studies. Improved completion efficiency is being tested with extended-reach jetting lance and other ultra-short radius lateral technologies. Improved completion efficiency, additional wells at closer spacing and better estimates of oil-in-place will result in additional oil production by primary and enhanced recovery processes.
The purpose of this project is to demonstrate targeted infill and extension drilling opportunities, better determinations of oil-in-place, methods for improved completion efficiency and the suitability of waterflooding in certain shallow-shelf carbonate reservoirs in the Williston Basin, Montana, North Dakota and South Dakota. Improved reservoir characterization utilizing 3-dimensional (3D) and multi-component seismic are being investigated for identification of structural and stratigraphic reservoir compartments. These seismic characterization tools are integrated with geological and engineering studies. Improved completion efficiency is being tested with short-lateral and horizontal drilling technologies. Improved completion efficiency, additional wells at closer spacing and better estimates of oil-in-place will result in additional oil production by primary and enhanced recovery processes.
Coal may be used to generate electrical energy by any of several processes, most of which involve combustion or gasification. Combustion in a coal-fired boiler and power generation using a steam-cycle is the conventional conversion method; however total energy conversion efficiencies for this type of process are only slightly over 30%. Integration of a gas-cycle in the process (combined cycle) may increase the total conversion efficiency to 40%. Conversion processes based on gasification offer efficiencies above 50%. H{sub 2}S is the predominant gaseous contaminant in raw coal gas. This process is concerned with the removal of H{sub 2} from coal gas through an electrochemical membrane technology.
The feasibility of continuous production of gallium arsenide ribbon single crystals, by passage of a molten zone through boron-oxide encapsulated GaAs feedstock, is being investigated. Polycrystalline GaAs ribbons have been grown in graphite boats by passage of a wide zone through B2O3-encapsulated feed-stock, confined by a quartz cover plate. Failure to remove the encapsulant above its glass transition temperature, however, resulted in cracking of the ribbons on cooling to room temperature. In order to study the crucial zone melting step in isolation from the encapsulation steps of the continuous process, a constrained-zone melting apparatus has been constructed in which the boron oxide serves only as a sealant to suppress arsenic vaporization. Large grained polycrystalline samples have been produced with this apparatus.
Electrostatic beneficiation of dry coal has received significant attention in the last decade. In this process the coal is ground and then charged, either by corona charging or by triboelectrification (friction charging). Coal and minerals receive different levels of charge -- often opposite polarities in the case of triboelectrification -- and can then be separated based on differences in electrical mobility. Problems associated with the techniques include rapid deposition of particles on the electrodes, thus, effecting further separation. The goal of this project is to optimize the electrostatic coal cleaning process to remove pyrites and inorganic materials through studies of the electrostatic properties of powdered coal, in-situ measurements of the electrodynamics of coal and mineral particles inside the separator, and development of self-cleaning collector plates for continuous separation.
This report is to present the progress made on the project ''Establishment of an Environmental Control Technology Laboratory (ECTL) with a Circulating Fluidized-Bed Combustion (CFBC) System'' during the period October 1, 2004 through December 31, 2004. The following tasks have been completed. First, the renovation of the new Combustion Laboratory and the construction of the Circulating Fluidized-Bed (CFB) Combustor Building have proceeded well. Second, the detailed design of supporting and hanging structures for the CFBC was completed. Third, the laboratory-scale simulated fluidized-bed facility was modified after completing a series of pretests. The two problems identified during the pretest were solved. Fourth, the carbonization of chicken waste and coal was investigated in a tube furnace and a Thermogravimetric Analyzer (TGA). The experimental results from this study are presented in this report. Finally, the proposed work for the next ...
This project seeks to produce sufficient information on the physical and chemical nature of Coolside waste to design and construct physically stable and environmentally safe landfills. Unconfined compressive strength and permeability tests are reported on samples remolded near 90, 95, and 100% of low energy, standard, and modified dry densities. Unconfined compressive strength tests were also performed on some of the samples after permeability tests were completed. Swell tests were initiated on samples from Coolside pilot plant run {number_sign}2 and on a FBC hydrated ash remolded near 95% of standard density and optimum moisture content.
Electric utility plants, for which construction commenced after September 18, 1978, must install and operate continuous emission monitoring (CEM) systems to demonstrate compliance with SO_2 and NO_x emission standards. Furthermore, effective December 4, 1987, each plant must develop and implement a CEM quality assurance (QA) program. This paper reviews the CEM and QA requirements set forth by new source performance standards (NSPS) promulgated by the Environmental Protection Agency. The paper summarizes operating characteristics of the 32 power plants currently subject to NSPS and describes the types of CEM systems used by these plants. Also, to the extent available, the paper presents the results of initial (i.e., first quarter 1988) QA activities (e.g., audits and calibration drift assessments) conducted by these plants.
A combination of erosion and corrosion at the Victoria Junction coal preparation plant in Sydney, Nova Scotia was causing serious problems. Schedule 80 mild steel pipes were starting to fail as well as some quarter-inch steel plates in the lauders and chutes. Some corrosion tests were carried out and the high chloride level in the process water was felt to be the single most important contribution to the corrosion problem. Cast basalt was selected as a solution to the pipe wear problem. Three different types of abrasion/corrosion-resistant tiling - basalt tiles, kalceram tiles and ceramic tiles were well suited to the chloride conditions at this plant.
The North Dakota Energy & Environmental Research Center (EERC) approach to removing NO{sub x} from flue gas emitted by coal-fired utility boilers or for the control of NO{sub x} formation by advanced combustion techniques involves the development of a catalytic fabric filter (CFF) for simultaneous NO{sub x} and particulate control. The NO{sub x}is removed by catalytic reduction with ammonia to form nitrogen and water. Bench-scale experimental results have shown that over 90% NO{sub x} removal can be achieved. This report details the strengths and areas for for development in this project.
This paper describes progress in several projects related to biomass power. These include switchgrass conversion development; switchgrass gasification development; production activities including soil studies, carbon studies, switchgrass production economics, watershed impacts, and prairie lands bio-products; information and education; and geographical information system. Attachments describe switchgrass co-firing test; switchgrass production in Iowa; cooperative agreements with ISU; Rathbun Lake watershed project; newspaper articles and information publications; Secretary of Agriculture Glickman`s visit; integration of technical aspects of switchgrass production in Iowa; and evaluation of an integrated biomass gasification/fuel cell power plant.
The major goal of this continuation project is to advance the utilization of heat transfer enhancement techniques in commercial heat exchange equipment. Thirteen heat transfer enhancement techniques have been identified as having potential for improving heat transfer coefficients in full-scale industrial equipment. The following tasks are part of this project, which was originally planned for three years: (1) expansion of technology information base; (2) evaluation of performance of enhanced surfaces and inserts; (3) correlation of data for spirally fluted surfaces; (4) study of structured surfaces in pool boiling; and (5) study of structured surface in spray film evaporation.
Raniganj and Jharia regions together have been for long the single largest coal supplier in India, now contributing about a quarter of the total output in the country. Numerous reasons such as improper mining techniques and policy, as well as unauthorized mining caused surface and subsurface coalfires in these areas. These coalfires burn millions of tonnes of valuable coal resources, creating severe environmental problems and posing enormous operational difficulties of mining. After first use of remote sensing as a tool to identify coalfires in 1960s, with the time, the efficiency of remote sensing to identify and monitoring coalfires has been well established by several researchers. With the knowledge of local geological setting and density sliced surface temperature image the spatial dis...
Psychological distress and postamputation pain were investigated in a sample of 582 males with long-term limb amputations (mean time since amputation 639.3 months, standard deviation 166.1; range 240-784 months). Prevalence of significant depressive symptoms (Hospital Anxiety and Depression Scale [HADS]-D score?8) was 32.0%, and 34.0% of respondents met the screening criterion for clinical anxiety (HADS-A score?8). Nearly one quarter (24.6%) of respondents reported significant post-traumatic psychological stress symptoms (Impact of Event Scale scores?35). In total, 87.8% experienced either phantom or residual limb pain. Affective distress scores differed according to the respondents' type of pain experience. Respondents who experienced residual limb pain reported significantly hig...
In the Advance Coal Liquefaction Concept Proposal (ACLCP) carbon monoxide (CO) and water have been proposed as the primary reagents in the pretreatment process. The main objective of this project is to develop a methodology for pretreating coal under mild conditions based on a combination of existing processes which have shown great promise in liquefaction, extraction and pyrolysis studies. The aim of this pretreatment process is to partially depolymerise the coal, eliminate oxygen and diminish the propensity for retograde reactions during subsequent liquefaction. The desirable outcome of the CO pretreatment step should be: (1) enhanced liquefaction activity and/or selectivity toward products of higher quality due to chemical modification of the coal structure; (2) cleaner downstream products; (3) overall improvement in operability and process economics.
To monitor the groundwater contamination and the effectiveness of remedial actions, over a thousand monitoring wells are in active operation (i.e., require quarterly or semi-annual sampling) at SRS. Most wells are expected to continue in operation for another 20 to 40 more years. Required sample volumes can range from a less than a liter to 10 liters. To support the long-term groundwater monitoring requirements of these wells, SRS actively seeks technologies that can maximize data acquisition and minimize costs. To meet this end, SRS has implemented the Purge Water Management System (PWMS). The key attributes of this system lie in its ability to reduce or eliminate the generation of purged groundwater, which is costly in terms of the time and management.
The six-axes industrial robot MANUTEC r15 UW was modified to work underwater and successfully tested down to the simulated water depth of 1100 m. Next step in the program was to use this robot as a handling tool for inspection tasks at the welding seam of an underwater structure conducted with CCD-cameras and distance sensors. This was also to demonstrate the possibility to assist and later on to replace divers from this work. Additional research was focussed on the stiffness and rigidity of the robot during the precise guiding of tools and workpieces under current water conditions up to a flow velocity of 1.1 m/s. Present work is concentrated on the application of this subsea robot on a maintenance task at the Brazilian underwater template OCTOS-1000. For this experiments the robot is integrated in a large mock-up which simulates a quarter section of this template. (orig.)
In the CERN approach to the design of a neutrino factory, the repetition frequency of the proton beam is high enough to consider stationary solid targets as a viable solution for multi-MW beams. The target consists of high density tantalum spheres of 2 mm diameter which can efficiently be cooled by passing a high mass flow He-gas stream through the voids between the Ta-granules. Very small thermal shocks and stresses will arise in this fine grained structure due to the relatively long burst of 3.3 ms from the SPL-proton linac. In a quadruple target system where each target receives only one quarter of the total beam power of 4 MW, conservative temperature levels and adequate lifetimes of the target are estimated in its very high radiation environment. A conceptual design of the integration of the target into the magnetic horn-pion-collector is presented.
New palladium(II) complexes (2), bearing NHC/TPPTS ligands, (NHC=benzimidazol-2-ylidene; TPPTS=triphenylphosphine-3,3',3''-trisulfonic acid trisodium salt) have been prepared and characterized by elemental analyses and spectroscopic methods. Their ability to catalyze the Suzuki-Miyaura reaction in neat water has been studied at 100^oC. Very high activities have been observed in the coupling of phenylboronic acid with aryl chlorides in the presence of 1% of the catalyst. We have compared the electronic properties of cis-[PdBr2(NHC)(TPPTS)] with the related complexes, [PdX2(NHC)]2 and [trans-PdBr2(NHC)(pdca)] (pdca=pyridine-2,6-dicarboxyic acid) (3) via three different techniques: cyclic voltammetry, thermogravimetric analysis and ^1^3C NMR spectroscopy.
One of the design targets for the ITER Tokamak Exhaust Processing system is not to lose more than 10{sup -5} g h{sup -1} into the Normal Vent Detritiation System of the Tritium Plant. The plasma exhaust gas, therefore, needs to be processed in a way that an overall tritium removal efficiency of about 10{sup 8} is reached. Such a high decontamination factor can only be achieved by multistage processes. The third step of the three step CAPER process developed at the TLK is based on a so-called permeator catalyst (PERMCAT) reactor, a direct combination of a Pd/Ag permeation membrane and a catalyst bed. The PERMCAT principle is based on isotopic swamping in a counter current mode. Previous tritium experiments employing laboratory scale PERMCAT reactors have revealed decontamination factors as high as 10{sup 5} for the third CAPER step. First tritium tests with a technical scale PERMCAT reactor led to similar decontamination factors and clearly ...
One of the design targets for the ITER Tokamak Exhaust Processing system is not to lose more than 10"-"5 g h"-"1 into the Normal Vent Detritiation System of the Tritium Plant. The plasma exhaust gas, therefore, needs to be processed in a way that an overall tritium removal efficiency of about 10"8 is reached. Such a high decontamination factor can only be achieved by multistage processes. The third step of the three step CAPER process developed at the TLK is based on a so-called permeator catalyst (PERMCAT) reactor, a direct combination of a Pd/Ag permeation membrane and a catalyst bed. The PERMCAT principle is based on isotopic swamping in a counter current mode. Previous tritium experiments employing laboratory scale PERMCAT reactors have revealed decontamination factors as high as 10"5 for the third CAPER step. First tritium tests with a technical scale PERMCAT reactor led to similar decontamination factors and clearly demonstrated that the ...
The investigation of various Two-Stage Liquefaction (TSL) process configurations was conducted at the Wilsonville Advanced Coal Liquefaction R D Facility between July 1982 and September 1986. The facility combines three process units. There are the liquefaction unit, either thermal (TLU) or catalytic, for the dissolution of coal, the Critical Solvent Deashing unit (CSD) for the separation of ash and undissolved coal, and a catalytic hydrogenation unit (HTR) for product upgrading and recycle process solvent replenishment. The various TSL process configurations were created by changing the process sequence of these three units and by recycling hydrotreated solvents between the units. This report presents a description of the TSL configurations investigated and an analysis of the operating and performance data from the period of study. Illinois No. 6 Burning Star Mine coal Wyodak Clovis Point Mine coal were processed. Cobalt-molybdenum and disposable iron-oxide ...
The bulk of the results from this project, besides being found in the research reports, are in the form of two theses presented for advanced degrees by two different students at two different institutions. Francis E. Porbeni is a Master`s Degree student in Chemistry at Clark Atlanta University and has prepared his Master`s Thesis entitled Simultaneous SO{sub 2} Oxidation and NO Decomposition over Copper Oxide on {gamma}-Alumina Catalysts: An Infrared Diffuse Reflectance Study. Sumit Rao, a Ph.D. student in Chemical Engineering at the Georgia Institute of Technology has defended his thesis entitled Role of Copper Ensemble Size in Silica and Zeolite Supported Catalysts for Nitric Oxide Decomposition. These two documents, which will be forwarded when final copies are available, provide the details of the bulk of the research accomplished over the duration of this project. These two documents are summarized, and other results from the project are ...
The knowledge shown in this work of the relationships between the oxidation stage of chromium, molybdenum and tungsten and their catalytic activity in some hydrocarbon reactions was achieved by the combination of separate investigations of reduction properties and the catalytic activity of the catalysts concerned. To characterize the electronic state of the reduced surfaces, X-ray photo-electronic spectroscopy was mainly used, supplemented by electron spin resonance. The catalyst activity was measured in conventional apparatus (flow, pulse and gradient-free reactors). (orig.) [Deutsch] Die in dieser Arbeit dargestellten Erkenntnisse ueber die Zusammenhaenge zwischen der Oxidationsstufe von Chrom, Molybdaen und Wolfram und ihrer katalytischen Aktivitaet in einigen Kohlenwasserstoffreaktionen wurden durch die Kombination getrennter Untersuchungen ueber Reduktionseigenschaften und katalytische Aktivitaet der betreffenden Katalysatoren erzielt. ...
CO poisoning is a major issue when reformate is used as a fuel in PEM fuel cells. Normally it is necessary to reduce the CO to very low levels (#approx#5 ppm) and CO tolerant catalysts, such as Pt-Ru, are often employed. As an alternative approach, we have studied the use of pulsed oxidation for the regeneration of CO poisoned cells. Results are presented for the regeneration of Pt and Pt-Ru anodes in a PEM fuel cell fed with CO concentrations as high as 10,000 ppm. The results show periodic removal of CO from the catalyst surface by pulsed oxidation can increase the average cell potential and increase overall efficiency. A method for enhancing the performance of a fuel cell stack using a microprocessor-based Fuel Cell Health Manager (FCHM) has been developed. The results of a cost/benefit analysis for the use of a FCHM on a 4 kW residential fuel cell system are presented. (author)
Certain materials, especially Sn, passivate the rare earth-exchanged Y zeolite (REY) used in petrochemical fluid-cracking catalysts against vanadium degradation caused by V impurities in the feed oil. The mechanism of passivation was investigated here from the standpoint of high-temperature oxide acid-base reaction; i.e., where the controlling factors were considered to be Lewis acid-base reactions between V{sub 2}O{sub 5}, the RE oxides, SnO{sub 2}, etc. Molten salt tests at 680{degree}C showed SnO{sub 2}, presumably because of its acidic nature, to be essentially nonreactive with V{sub 2}O{sub 5} or Na{sub 2}O-V{sub 2}O{sub 5} compounds. A hypothesis was developed to explain how the passivation effect by Sn might result from the unique resistivity of SnO{sub 2} to reaction with V{sub 2}O{sub 5}.
This final report summarizes the results of our research under Contract No. DE-AC22-92PC92112, Novel Catalysts for Methane Activation. In this research we prepared and tested fullerene soots for converting methane into higher hydrocarbons. We conducted the methane conversions using dehydrocoupling conditions, primarily in the temperature regimes of 600{degrees}-1000{degrees}C and atmospheric pressures. The research was divided into three sections. The first section focused on comparing fullerene soots with other forms of carbon such as acetylene black and Norit-A. We found that the fullerene soot was indeed more reactive than the other forms of carbon. However, due to its high reactivity, it was not selective. The second section focused on the effect of metals on the reactivity of the soots, including both transition metals and alkali metals. We found that potassium could enhance the selectivities of fullerene soot to higher hydrocarbons, but the effect was unique ...
This paper reports on the superiority of zeolites over amorphous solids which is well documented for solid acid catalysts of industrial use. Crystalline supports, likewise, open attractive perspectives for catalysis by metals, alloys, and ligated metal clusters. Size and location of clusters can be controlled by careful design of the preparation conditions. Pore dimensions control the access of reactants to active sites and escape paths for products. Cage dimensions determine which transition states can be attained; window apertures are functional in isolating metal clusters from each other, thus preventing ther coalescence and growth. The ship-in-a-bottle method permits deisgn of fairly large active complexes entrapped in zeolite cages. Orientation of non-spherical molecules in a zeolite proe helps to direct their collision with a metal particle to the head on mode; however, isolated Pt atoms hidden in niches of the pore walls can attack passing molecules at their ...
The lipid obtained by the toluene extraction of a dried raw Atlanta sewage sludge by the Soxhlet method, was pyrolyzed over activated alumina at atmospheric pressure. A range of weight hourly space velocities (WHSV) from 0.22-1.60/h and a range of temperatures from 400-480[degree]C were selected. A 70 wt % yield of light liquid hydrocarbons was obtained at a WHSV of 0.46/h and 450[degree]C. The sulfur and nitrogen contents of the pyrolysis products were much lower than products from direct liquefaction of sludge. Infrared spectra and [sup 13]C nuclear magnetic resonance confirmed the absence of carbonyl groups in the products. Gas chromatography showed a uniform hydrocarbon chain length distribution across the C[sub 7] to C[sub 17] mass range. The gas product consisted mainly of carbon dioxide and hydrocarbons. Lauric acid was used as a model to study the decarboxylation. The effects of catalyst loading and catalyst moisture content were ...
Nine coals from Spanish, British, German and American mining basins were hydrogenated using Fe catalyst precursors (red mud and FeSO{sub 4}), without solvent at 300, 350, and 400 {degree}C and 10 MPa of H{sub 2}. Overall conversion and product distribution are related to the textural characteristics of the original coals and are studies throughout the distinct hydrogenation processes. Results reveal that with FeSO{sub 4} as a catalyst precursor, conversions increase with coal surface area. However, when red mud (RM) is used, conversions are independent of coal textural characteristics. Higher conversions are obtained with FeSO{sub 4} than with RM at 300 and 350 {degree}C whereas at 400 {degree}C higher conversions are obtained with RM. This different catalytic activity is also reflected in the changes of the textural characteristics observed in each case. Up to 350 {degree}C, the residues from FeSO{sub 4}-catalyzed processes reveal increased ...
This paper describes the development of a computational multiphase fluid dynamics (CMFD) model of the Fischer Tropsch (FT) process in a Slurry Bubble Column Reactor (SBCR). The CMFD model is fundamentally based which allows it to be applied to different industrial processes and reactor geometries. The NPHASE CMFD solver [1] is used as the robust computational platform. Results from the CMFD model include gas distribution, species concentration profiles, and local temperatures within the SBCR. This type of model can provide valuable information for process design, operations and troubleshooting of FT plants. An ensemble-averaged, turbulent, multi-fluid solution algorithm for the multiphase, reacting flow with heat transfer was employed. Mechanistic models applicable to churn turbulent flow have been developed to provide a fundamentally based closure set for the equations. In this four-field model formulation, two of the fields are used to track the gas phase (i.e., small spherical and ...
In the past three years, we followed the work plan as we suggested in the proposal and made every efforts to fulfill the project objectives. Based on our large amount of creative and productive work, including both of experimental and theoretic aspects, we received important technical breakthrough on naphthenic acid removal process and obtained deep insight on catalytic decarboxylation chemistry. In detail, we established an integrated methodology to serve for all of the experimental and theoretical work. Our experimental investigation results in discovery of four type effective catalysts to the reaction of decarboxylation of model carboxylic acid compounds. The adsorption experiment revealed the effectiveness of several solid materials to naphthenic acid adsorption and acidity reduction of crude oil, which can be either natural minerals or synthesized materials. The test with crude oil also received promising results, which can be potentially developed into a ...
The necessary conditions to design the methanol-fueled direct injection diesel engine with a reservoir type glow plug were cleared up from the points of view to prevent the air contamination and to use as an alternative oil for automotives, and as a result the good engine performance and emission characteristics could be obtained under the wide operating condition. The following facts were clarified: It is necessary to arrange the glow plug on the line of atomizing axis near the nozzle hole to ensure the ignitability under a wide operating condition. The reservoir type glow plug which reserves the premixed gas around the glow plug can shorten the ignition delay time and improve the combustion stability and the net thermal efficiency in the light load region. The combustion in the light load region was accelerated, NO{sub x} emission rate was suppressed and moreover, the net thermal efficiency and catalyst conversion rate were improved by applying an EGR(exhasut gas ...
For the removal and recycle of CO2, a global warming gas, utilization of photosynthesis by micro algae is investigated. Formed micro algae are decomposed into CO2, H2O and CH4 again, which does not result in the permanent fixation. For the effective utilization of these micro algae, creation of petroleum alternate energy was tried through the co-liquefaction of micro algae with coal. Were investigated influences of the reaction temperature during the co-liquefaction and influences of catalysts, such as Fe(CO)5-S, Ru(CO)12, and Mo(CO)6-S, which are effective for the coal liquefaction. Micro algae, such as chlorella, spirulina, and littorale, and Yallourn brown coal were tested. It was found that co-liquefaction of micro algae with coal can be successfully proceeded under the same conditions as the liquefaction of coal. The oil yield obtained from the co-liquefaction in the presence of Fe(CO)5-S, an effective catalyst for coal liquefaction, ...
This report presents the results of Run 260 performed at the Advanced Coal Liquefaction R&D Facility in Wilsonville. The run was started on July 17, 1990 and continued until November 14, 1990, operating in the Close-Coupled Integrated Two-Stage Liquefaction mode processing Black Thunder mine subbituminous coal (Wyodak-Anderson seam from Wyoming Powder River Basin). Both thermal/catalytic and catalytic/thermal tests were performed to determine the methods for reducing solids buildup in a subbituminous coal operation, and to improve product yields. A new, smaller interstage separator was tested to reduce solids buildup by increasing the slurry space velocity in the separator. In order to obtain improved coal and resid conversions (compared to Run 258) full-volume thermal reactor and 3/4-volume catalytic reactor were used. Shell 324 catalyst, 1/16 in. cylindrical extrudate, at a replacement rate of 3 lb/ton of MF coal was used in the catalytic stage. Iron oxide ...
This report presents the results of Run 260 performed at the Advanced Coal Liquefaction R D Facility in Wilsonville. The run was started on July 17, 1990 and continued until November 14, 1990, operating in the Close-Coupled Integrated Two-Stage Liquefaction mode processing Black Thunder mine subbituminous coal (Wyodak-Anderson seam from Wyoming Powder River Basin). Both thermal/catalytic and catalytic/thermal tests were performed to determine the methods for reducing solids buildup in a subbituminous coal operation, and to improve product yields. A new, smaller interstage separator was tested to reduce solids buildup by increasing the slurry space velocity in the separator. In order to obtain improved coal and resid conversions (compared to Run 258) full-volume thermal reactor and 3/4-volume catalytic reactor were used. Shell 324 catalyst, 1/16 in. cylindrical extrudate, at a replacement rate of 3 lb/ton of MF coal was used in the catalytic stage. Iron oxide was ...
The investigations showed that the new adsorber/catalyst composites are well suited for chemical degradation of persistent water pollutants. Compared with alternative processes, the reaction selectivity and the consumption of oxidant are more favourable as the reaction now takes place on/inside the solid. The process, which was developed originally for purification of contaminated water, can be transferred to many other systems of materials. For example, it is expected that the soot emissions of diesel engines will be reduced significantly after efficient hydrogenation of the aromatics contained in the diesel engine on molybdenum-charged mesoporous composites. [German] Mit den vorliegenden Untersuchungen konnte ein erster Nachweis gefuehrt werden, dass die neu entwickelten Adsorber/Katalysator-Komposite fuer den chemischen Abbau persistenter Wasserschadstoffe geeignet sind. Im Vergleich zu alternativen Verfahrensloesungen kann die Selektivitaet der Reaktion und der ...
This report contains two sections. In the first section a limited review is presented and the preparation of the red mud based additives is described. The additives are characterized by composition and their catalytic activity in hydrocracking is investigated in a batch autoclave under an initial hydrogen pressure of 12 MPa at 435 C and 30 min residence time. A quantitative characterization of the products is given. Comparisons between the red mud additives and coke respectively a commercial catalyst are made. (orig.)
Research activity during the 1991--1992 funding period has been concerned with the following topics relevant to carbon monoxide activation. (1) Exploratory studies of water gas shift catalysts heterogenized on polystyrene based polymers. (2) Mechanistic investigation of the nucleophilic activation of CO in metal carbonyl clusters. (3) Application of fast reaction techniques to prepare and to investigate reactive organometallic intermediates relevant to the activation of hydrocarbons toward carbonylation and to the formation of carbon-carbon bonds via the migratory insertion of CO into metal alkyl bonds.
Research activity during the 1991--1992 funding period has been concerned with the following topics relevant to carbon monoxide activation. (1) Exploratory studies of water gas shift catalysts heterogenized on polystyrene based polymers. (2) Mechanistic investigation of the nucleophilic activation of CO in metal carbonyl clusters. (3) Application of fast reaction techniques to prepare and to investigate reactive organometallic intermediates relevant to the activation of hydrocarbons toward carbonylation and to the formation of carbon-carbon bonds via the migratory insertion of CO into metal alkyl bonds.
The methods of diffuse-reflection optical spectroscopy and EPR were used to study the state of molybdenum in catalysts prepared by impregnating ultrastable zeolite with molybdenum salt solutions and by mixing in the solid phase with MoCl/sub 5/. It has been shown that molybdenum introduced into zeolites in small amounts is found basically in the form of isolated hexavalent ions of molybdenum. In addition, Mo/sup 5 +/ and Mo/sup 4 +/ ions are also present. Heteropolycompounds also form. The molybdenum ions are most readily reduced in the zeolite prepared by impregnation with a solution of ammonium paramolybdate.
;Table of Contents: Gaseous Pollutants Emissions from Coal Combustors and Their Control Technologies in Japan; Simultaneous Determination of Cooper (II) and Iron (III) Using 8-Quinolinol by Solvent Extraction Flow-injection Method; Fundamental Studies on Red Mud as a Catalyst for Coal Liquefaction: Studies on Active Components in Red Mud and Possibilities for Improvement of Its Catalytic Activities; Elution Behavior of Coal-derived Liquids with Sephadex LG-20; Characteristic of Activated Carbon Produced from Scrap Tires at Different Activation Temperatures; Energy Saving Snow Melting System.
According to W. H. Wiser and A. G. Oblad, the program at the University of Utah to develop coal conversion techniques, which has received federal grants of $1.35 million since 1969, recently was awarded $425,000 from the U.S. Office of Coal Research for the development of catalysts for coal conversion and low-sulfur fuel oil production. In tests, 100 lb of coal have been converted into 95 lb of products composed of 30 lb liquid fuel like gasoline, 5 lb of diesel or fuel oil, 30 lb of gaseous fuel, and 30 lb of char.
A process for the production of transportation fuels from heavy hydrocarbonaceous feedstock is provided comprising a two-stage, close-coupled process, wherein the first stage comprises a hydrothermal zone into which is introduced a mixture comprising a feedstock and red mud having coke-suppressing and demetalizing activity, and hydrogen; and the second, close-coupled stage comprises a hydrocatalytic zone into which substantially all the effluent from the first stage is directly passed and processed under hydrocracking conditions.
The method of programmed thermodesorption has been used to study the forms of hydrogen adsorption in ZrNiHsub(x) hydride. It is shown that high concentration of the hydrogen, which extracted from hydride in the temperature range of 240-260 deg C results in appearance of ''reverse'' peak. Charge of hydride adsorption properties during its oxidation-reduction treatment is studied. Comparison with spectra of hydrogen thermodesorption from the surface of Ni/ZrO_2 deposited catalyst and zirconium oxide is carried out.
A process is claimed for selectively preparing a mixture of two-carbon atom oxygenated hydrocarbons, namely, acetic acid, ethanol and acetaldehyde, by continuously contacting a gaseous reaction mixture containing hydrogen and carbon monoxide with a solid catalyst comprising rhodium in combination with one or more alkali metals selected from the group consisting of lithium, potassium, cesium and rubidium at reaction conditions correlated so as to favor the formation of a substantial proportion of such two-carbon atom products.
Doped ultrafine silicon dioxide powder with a narrow particle size distribution was obtained by RF discharge-stimulated dichlorosilane (SiH2C) oxidation at a low pressure using isobutylene as the combustion inhibitor and chromium hexacarbonyl (Cr(CO)6) as the dopant. The formation and morphology of the ultrafine particles are governed by the parameters of the RF discharge and by the chemical mechanism of the combustion reaction yielding the aerosol. Submicron-sized filamentous carbon structures can be obtained by isobutylene decomposition under spark discharge conditions in the presence of a molybdenum metal catalyst.
The partial oxidation of 1,3-butadiene has been investigated over VMoO catalysts synthesized by sol-gel techniques. Surface areas were 9-14 m{sup 2}/g, and compositions were within the solid solution regime, i.e. below 15.0 mol % MoO{sub 3}/(MoO{sub 3} + V{sub 2}O{sub 5}). Laser Raman Spectroscopy and XRD data indicated that solid solutions were formed, and pre- and post-reaction XPS data indicated that catalyst surfaces contained some V{sup +4} and were further reduced in 1,3-butadiene oxidation. A reaction pathway for 1,3-butadiene partial oxidation to maleic anhydride was shown to involve intermediates such as 3,4-epoxy-1-butene, crotonaldehyde, furan, and 2-butene-1,4-dial. The addition of water to the reaction stream substantially increased catalyst activity and improved selectivity to crotonaldehyde and furan at specific reaction temperatures. At higher water addition concentrations, furan selectivity increased from ...
Zeolite Y is the active component of most commercial cracking catalysts. Interaction of H[sub 3]PO[sub 4] with extraframework aluminum of ultra-stable zeolite (USY) leads to the formation of different types of aluminum phosphates, while there is no indication of the formation of SAPO zeotype structures. The total acidity of USY slightly decreases upon the H[sub 3]PO[sub 4] treatment, while the maximum in the distribution of acid strength is shifted to milder acidities. Dealumination of the zeolite and creation of POH sites associated with AIPO[sub 4] are responsible for the modifications observed. 37 refs., 8 figs., 3 tabs.
Several possibilities of the use of molecular models in quantum-chemical investigations of the structure of defect centers on the surfaces of oxides on nontransition elements have been illustrated. There has been a special discussion of the assumption of the local nature of the chemical interactions in these systems, which underlies such an approach, and of the consequent laws governing the formation of their lattices in the example cases of zeolites, kaolinites, and comparable boron- and aluminum-containing oxides. A quantum-chemical interpretation of the body of experimental data from investigations of the dehydroxylation of H forms of zeolites has been given. The structure of the Lewis acid centers formed as a result, and their chemisorption properties, have been discussed.
In order to improve the handling capability of red mud, it is mixed with fine-grain coal material such as brown coal or lignite in dust form, in a ratio by weight of between 0.5-10:1. The liquid present in the red mud is bound by the very fine coal admixed therewith so that the resulting mixture can be stored in a silo and even pneumatically conveyed, and the oily properties of the red mud are removed by the treatment. The mixture is particularly suitable for use in connection with the hydrogenating liquefaction of coal in which the red mud is used as a catalyst.
A process for the production of transportation fuels from heavy hydrocarbonaceous feedstock is provided comprising a two-stage, close-coupled process, wherein the first stage comprises a hydrothermal zone into which is introduced a mixture comprising a feedstock and metals-impregnated red mud having coke-suppressing and demetalizing activity, and hydrogen; and the second, close-coupled stage comprises a hydrocatalytic zone into which substantially all the effluent from the first stage is directly passed and processed under hydrocatalytic conditions. The preferred metals for impregnation include transition metals, in particular, nickel and molybdenum.
Scientists of the Institute of Wood Chemistry of the Latvian Academy of Sciences have developed two highly efficient processes for producing furfural, a feedstock for varnishes, synthetic resins and plastics. It is made of production wastes, including branches and small-dimension timber. By one process, the raw material is chipped, treated first with diluted sulphuric acid and then with steam heated to 250 degrees C. The other uses concentrated sulphuric acid as a catalyst. Besides furfural, this process also yields sugar solutions used in alcohol and nutrient yeast production.
Four high-sulphur low-rank coals have been treated at hydrogenation conditions with three iron-based catalyst precursors: Red Mud (Fe[sub 2]O[sub 3]), iron sulphide and iron pentacarbonyl. The obtained yields show a dependence with the sulphur content of the coals; the organic sulphur content correlates with the conversion and THF-solubles when Red Mud and iron sulphide are added. In spite of the high hydrogen sulphide partial pressure in the reaction, the addition of other sources of sulphur enhances the percentages in conversion products. 15 refs., 2 figs., 3 tabs.
We have investigated the stability and catalytic activity of epitaxial overlayers of rhodium on Au(111) and Pd(111). Both surfaces show a strong affinity for hydrogen. We have calculated the energy of adsorption both for a strongly and a more weakly adsorbed species; the latter is the intermediate in the hydrogen evolution reaction. Both the energy of activation for hydrogen adsorption (Volmer reaction) and hydrogen recombination (Tafel reaction) are very low, suggesting that these overlayers are excellent catalysts. PMID:21847482
The key component for improving the energy efficiency and cycle life of the electrically rechargeable zinc-air battery is the bifunctional air electrode. The air electrodes described in this paper contained different types of carbon black as the substrate for the perovskite catalyst (La{sub 0.6}Ca{sub 0.4}CoO{sub 3}). Morphological and physical properties of the carbon substrates play an important role in enhancing the activity and stability of the bifunctional air electrode. Current-potential curves and cycle-life tests were applied in order to gather information on the activity and stability of these electrodes. (authors)
The Balandin type volcano plots have been considered for the main criterion both in catalysis and electrocatalysis to estimate their fundamental properties and optimal activity: ({alpha}) The ones, when some physical feature or catalytic activity itself is plotted usually along transition series, and ({beta}) The others, when catalytic activity arises as a function of some energetic property, the most usually of the adsorption enthalpy of intermediates bonding upon the substrate in the rate determining step (rds). 29 refs.
In 1980 Sasol completed its very large coal conversion complex, Sasol Two and Three in South Africa. This complex, the largest coal-to-liquids facility in the world, utilizes Sasol's proprietary Fischer-Tropsch technology, the Synthol Process. The two key elements of the Synthol Process are its catalyst and its unique fluidized bed reactor, the Synthol Circulating Fluidized Bed Reactor. Details on the catalytic aspects and reaction mechanism have been given elsewhere. In this paper, the history of the development of the reactor is discussed.
Air pollution abatement measures are being intensified at the moment: Power plants and district heating systems are being retrofitted with high-efficiency desulphurisation and NO/sub 2/ reduction systems, the 3rd amendment of the Clean Air Technical Guide sets more rigid emission limits, and unleaded petrol and catalysts will significantly reduce car exhaust emissions. The author presents pollutant balances from 1966 to 1982 to contradict the popular notion that pollutant emitters formerly failed to take preventive measures.
The performance of a solar chemical heat pipe was studied using CO{sub 2}reforming of methane as the endothermic reaction. A directly heated vertical reactor, packed with a rhodium catalyst was used. The solar tests were carried out in the Schaeffer solar furnace of the Weizmann Institute of Science. The power absorbed was up to 6.3 KW, the maximal flow rates of the gases reached 11,000 1/h, and the methane conversions reached 85%. A computer model was developed to simulate the process. Agreement of the calculations with the experimental results was quite satisfactory.
A process is provided for conducting organic compound conversion over a catalyst composition comprising a specially treated crystalline zeolite having a high initial silica-to-alumina mole ratio, said zeolite having been synthesized from a reaction mixture comprising a diamine as a cation source. The treatment of the zeolite material comprises the sequential steps of reacting the zeolite with a dilute hydrogen fluoride solution, contacting the hydrogen fluoride solution reacted material with aluminum chloride vapor, and then treating the aluminum chloride contacted material to convert it to hydrogen form.
Badger (Cambridge, MA) and Mobil (Fairfax, VA) are ready to jointly license a new cumene technology that they say achieves higher yields and product purity than existing processes. The zeolite-based technology is scheduled to be introduced at next month's DeWitt Petrochemical Review in Houston. The Mobil/Badger technology aims to challenge the dominant position of UOP's (Des Plaines, IL) solid phosphoric acid (SPA) catalyst process - which accounts for 80%-90% of the world's cumene production. In addition, Monsanto/Kellogg's aluminum chloride-based technology has gained significant momentum since its introduction in the 1980s. And late last year, ABB Lummus Crest (Bloomfield, NJ) also began marketing a zeolite-based cumene technology. While all the technologies make cumene via the alkylation of benzene with propylene, the Mobil/Badger process uses a zeolite-containing catalyst designed by Mobil to selectively ...
Hydrocarbon synthesis during CO hydrogenation over Pd/M-ZSM5 (M=H,Na,La) and Pd/SiO/sub 2/ has been investigated. Overall activity depended on the cation-exchanged form of the support and decreased in the order Pd/La-ZSM5 = Pd/Na-ZSM5 > Pd/H-ZSM5 > Pd/SiO/sub 2/. The zeolite-supported catalysts showed high selectivity towards saturated C/sub 2/-C/sub 6/ hydrocarbons, whereas Pd/SiO/sub 2/ favored methanol production. Increasing temperature and H/sub 2//CO feed ratio led to higher reaction rates, lower yields of C/sub 2/-C/sub 6/ products, and increased lighter hydrocarbons. A mechanical mixture of Pd/SiO/sub 2/ and Na-ZSM5 showed similar product distribution as Pd/Na-ZSM5. Infrared spectra of the catalysts under reaction conditions indicate the presence of adsorbed oxygenates on the zeolite. Changes in the IR bands during the initial stages of the reaction suggest that surface species on the zeolite are not methanol synthesis ...
Rhodium (Rh) is a critical component of current automotive three-way catalysts (TWCs), particularly with regard to NO{sub x} and CO conversion at rich and stoichiometric air-fuel ratios (A/F). Rh supported on CeO{sub 2} was active for NO{sub x} and CO conversions but could be deactivated easily by high temperature aging. The cause of the deactivation is ascribed to the sintering of CeO{sub 2}. ZrO{sub 2} incorporation into CeO{sub 2} is reported to have high thermal durability in terms of oxygen storage capacity (OSC). There has been no report showing direct experimental evidence that Rh-loaded on CeO{sub 2}-ZrO{sub 2} mixed oxides induced effects on TWC performance improvement in the actual automotive exhaust. In the present paper, the Rh-CeO{sub 2} interaction contributing to NO{sub x} reduction and the catalytic behavior of Rh-loaded CeO{sub 2}-ZrO{sub 2} mixed oxide is addressed. Incorporating CeO{sub 2}-ZrO{sub 2} into a catalyst offered ...
This award provided for an automated computer-controlled goniometer/diffractometer/manipulator with hot and cold stages and data acquisition system that was interfaced with the high resolution Scienta ESCA-300 X-ray photoelectron spectrometer at Lehigh University. The automation allows angular dependent X-ray photoelectron spectroscopy (XPS) and ultraviolet photoelectron spectroscopy (UPS) data to be accurately and rapidly collected without the very time-consuming and labor-intensive manual method that was previously required. It also provides for automated multi-sample analyses, collecting both wide survey scans and selected binding energy range analyses, with complete computer control and data storage. This allows 24 hour data collection without requiring the continuous presence of operators. The overall result is a greater productivity for the XPS laboratory, approximately doubling the output of the laboratory. While the automated computer-controlled goniometer/manipulator with ...
The overall purpose of this project is to evaluate the biological and economic feasibility of restoring high-quality forests on mined land, and to measure carbon sequestration and wood production benefits that would be achieved from forest restoration procedures. In this quarterly report, we present a preliminary comparison of the carbon sequestration potential of forests growing on 14 mined sites in a seven-state region in the Midwestern and Eastern Coalfields. Carbon contents of these forests were compared to adjacent forests on non-mined land. The study was installed as a 3 x 3 factorial in a random complete block design with three replications at each location. The treatments include three forest types (white pine, hybrid poplar, mixed hardwood) and three silvicultural regimes (competition control, competition control plus tillage, competition control plus tillage plus fertilization). Each individual treatment plot is 0.5 acres. Each block of nine plots ...
Accomplishments for the quarter are presented for the following areas of research: oil shale, tar sand, coal, advanced exploratory process technology, and jointly sponsored research. Oil shale research includes; oil shale process studies, environmental base studies for oil shale, and miscellaneous basic concept studies. Tar sand research covers process development. Coal research includes; underground coal gasification, coal combustion, integrated coal processing concepts, and solid waste management. Advanced exploratory process technology includes; advanced process concepts, advanced mitigation concepts, and oil and gas technology. Jointly sponsored research includes: organic and inorganic hazardous waste stabilization; development and validation of a standard test method for sequential batch extraction fluid; operation and evaluation of the CO{sub 2} HUFF-N-PUFF Process; fly ash binder for unsurfaced road aggregates; solid state NMR analysis of Mesa Verde Group, ...
This fourteenth quarterly technical progress report of the MHD Integrated Topping Cycle Project presents the accomplishments during the period November 1, 1990 to January 31, 1991. Testing of the High Pressure Cooling Subsystem electrical isolator was completed. The PEEK material successfully passed the high temperature, high pressure duration tests (50 hours). The Combustion Subsystem drawings were CADAM released. The procurement process is in progress. An equipment specification and RFP were prepared for the new Low Pressure Cooling System (LPCS) and released for quotation. Work has been conducted on confirmation tests leading to final gas-side designs and studies to assist in channel fabrication.The final cathode gas-side design and the proposed gas-side designs of the anode and sidewall are presented. Anode confirmation tests and related analyses of anode wear mechanisms used in the selection of the proposed anode design are presented. Sidewall confirmation ...
This report describes the progress made during the second Quarter of a two year project to demonstrate that the air pollution, from a traveling grate stoker being used to heat water at a central heating plant in Krakow Poland, can be reduced significantly by replacing the unwashed, unsized coal now being used with a mechanically cleaned, double sized stoker fuel and by optimizing the operating parameters of the stoker. It is anticipated that these improvements will prove to be cost effective and hence be adopted in the other central heating plants in Krakow and indeed throughout Eastern European cities where coal is the primary source of heating fuel. EFH Coal Company has formed a partnership with two Polish institutions -- MPEC a central heating company in Krakow and Naftokrak-Naftobudowa, preparation plant designers and fabricators for this effort. The washability data from a 20mm x 0.5mm size fraction of raw coal from the Staszic Mine were evaluated. The data ...
During the second half of 1993, the groundwater at the F-Area Seepage Basins (FASB) was monitored in compliance with Module 3, Section C, of South Carolina Hazardous Waste Permit SC1-890-008-989, effective November 2, 1992. The monitoring well network is composed of 87 FSB wells screened in the three hydrostratigraphic units that make up the uppermost aquifer beneath the FASB. A detailed description of the uppermost aquifer is included in the Resource Conservation and Recovery Act Part B post-closure care permit application for the F-Area Hazardous Waste Management Facility submitted to the South Carolina Department of Health and Environmental Control (SCDHEC) in December 1990. Beginning in the first quarter of 1993, the standard for comparison became the SCDHEC Groundwater Protection Standard (GWPS) specified in the approved F-Area Seepage Basins Part B permit. Currently and historically, gross alpha, nitrate, nonvolatile beta, and tritium are among the primary ...
The objectives of this project are to support the DOE direct coal liquefaction process development program and to improve the useful application of analytical chemistry to direct coal liquefaction process development. Independent analyses by well-established methods will be obtained of samples produced in direct coal liquefaction processes under evaluation by DOE. Additionally, analytical instruments and techniques which are currently underutilized for the purpose of examining coal-derived samples will be evaluated. The data obtained from this study will be used to help guide current process development and to develop an improved data base on coal and coal liquids properties. A sample bank will be established and maintained for use in this project and will be available for use by other researchers. The reactivity of the non-distillable resids toward hydrocracking at liquefaction conditions (i.e., resid reactivity) will be examined. From the literature and data experimentally obtained, ...
Energy from biomass is a CO{sub 2} neutral, sustainable form of energy. Anaerobic digestion is an established technology for converting biomass to biogas, which contains around 60% methane, besides CO{sub 2} and various contaminants. Most types of biomass contain material that cannot be digested; in woody biomass, this portion is particularly high. Therefore, conventional anaerobic digestion is not suited for the production of biogas from woody biomass. While wood is already being converted to energy by conventional thermal methods (gasification with subsequent methanation), dung, manure, and sewage sludge represent types of biomass whose energy potential remains largely untapped (present energetic use of manure in Switzerland: 0.4%). Conventional gas phase processes suffer from a low efficiency due to the high water content of the feed (enthalpy of vaporization). An alternative technology is the hydrothermal gasification: the water contained within the biomass serves as reaction ...
The catalytic oxygen transfer properties of vanadium containing zeolites and vanadium based sol-gel catalysts with hydrogen peroxides are well known. The severe problem of vanadium leaching caused by the presence of the by-product water has been addressed. To avoid any interference with homogeneously catalyzed reactions, our study focusses on selective oxidations in a moisture-free medium with tert.-butylhydroperoxide. We have investigated the catalytic properties of amorphous microporous materials based on SiO{sub 2}, TiO{sub 2}, ZrO{sub 2} and Al{sub 2}O{sub 3} as matrix material and studied the effects of surface polarity on the oxidation of 1-octene and cyclohexane. (orig.)
An experimental and modelling study was performed for a reverse flow catalytic converter attached to a natural gas/diesel dual fuel engine. The catalytic converter had a segmented ceramic monolith honeycomb substrate and a catalytic washcoat containing a predominantly palladium catalyst. A one-dimensional single channel model was used to simulate the operation of the converter. The kinetics of the CO and methane oxidation followed first-order behaviour. The activation energy for the oxidation of methane showed a change with temperature, dropping from a value of 129 to 35 kJ/mol at a temperature of 874 K. The reverse flow converter was able to achieve high reactor temperature under conditions of low inlet gas temperature, provided that the initial reactor temperature was sufficiently high. (author)
The effect of chemical pretreatments using NaOH, H2O2, and Ca(OH)2 on Empty Palm Fruit Bunches (EPFB) to degrade EPFB lignin before pyrolyis was investigated. Spectrophotometer analysis proved consecutive addition of NaOH and H2O2 decomposed almost 100% of EPFB lignin compared to 44% for the Ca(OH)2, H2O2 system while NaOH and Ca(OH)2 used exclusively could not alter lignin much. Next, the pretreated EPFB was catalytically pyrolyzed. Experimental results indicated the phenolic yields over Al-MCM-41 and HZSM-5 catalysts were 90wt% and 80wt%, respectively compared to 67wt% yield for the untreated sample under the same set of conditions. Meanwhile, the experiments with HY zeolite yielded 70wt% phenols.
The development of 'Green Chemistry' requires new materials to replace the conventional organic chemistry by biological catalysts, to produce fine chemicals in an environmentally friendly manner. Microbial whole cells can be directly used as biocatalysts, providing a simple and cheap methodology since enzyme isolation and purification are avoided. High-density polyethylene (HDPE) is a very stable polymer though it can be activated by gamma radiation to induce grafting. Glycidyl methacrylate was grafted onto macroporous HDPE and PP in the range of 1-6%, proportional to the initial monomer concentration. Grafted polymers were further chemically modified with ethylenediamine to generate a cationic hydrogel of micron-size thickness onto the internal polymer surfaces. Modified polymers were able to immobilize Gram-positive and Gram-negative bacteria that can catalyze a chemical reaction as efficient as free cells do.
The proposed active sites on the catalyst surface in heterogeneous propylene ammoxidation have been successfully modelled by structurally characterized pinacolato W(VI) tert-butylimido complexes. These compounds exist as an equilibrating mixture of amine-bis(imido) and imido-bis(amido) complexes, the position of this equilibrium is dependent on the electronic nature of the glycolate ligand. Both of the C-N bond-forming reactions proposed in recent studies by Grasselli et al. (1) have been reproduced using discrete Group VI d{sup 0} organoimido complexes under mild conditions suitable for detailed mechanistic studies. These reactions are: (1) oxidative trapping of radicals at molybdenum imido sites, and (2) migration of the allyl group from oxygen to an imido nitrogen atom.
Two transition metal ions (Cu^2^+ and Co^2^+) and two rare earth metal ions (Ce^3^+ and La^3^+) were used as the assisted metal ions, respectively to prepare the transition metal and rare metal assisted Fe bimetallic amidoximated polyacrylonitrile (AO-PAN) fiber complexes. And their coordination configuration and visible light adsorption properties were examined by coordination number determination and UV-vis-DRS. Then the catalytic performance of these complexes was evaluated as the heterogeneous Fenton catalysts in Rhodamine B degradation by changing the nature and dosage of the assisted ions added. The results indicated that the incorporation of the assisted metal ions led to Fe bimetallic AO-PAN complexes with the more unsaturated configurations than Fe monometallic AO-PAN complex due ...
This report accounts for Task 3 of DOE Contract No. AC01-81FE-05077. It reviews the developments in indirect coal liquefaction with emphasis on slurry-phase reactors and catalysis. This report also discusses topics related to indirect coal liquefaction research, such as analytical techniques in catalysis. The subjects covered in this report were selected by DOE. This report is the third and final task report of the three major tasks in this contract. The first task, ''Direct Coal Liquefaction Catalyst Development - Program Review and Research Perspectives'', was completed in November 1982. The second task, ''Review of Direct Coal Liquefaction by Slurry-Phase Catalysis'', was completed in September 1983. 47 refs., 66 figs., 50 tabs.
Pulse reactor experiments were conducted on the reactions of unlabeled or deuterium- or oxygen-18-labeled allyl alcohols over molybdenum trioxide and various bismuth molybdates in the absence or presence of oxygen and ammonia. The allyl alcohol apparently adsorbed on oxidation sites to form acrolein via allyl molybdates, and on Broensted acid sites to form diallyl ether via an allyl carbonium ion. The bismuth enhanced ..cap alpha..-hydrogen abstraction, which was the rate-determining step in the oxidation. The product distributions provided evidence that the selective oxidation of propylene to acrolein proceeds via a m-allyl molybdate which collapses to an O o-allyl molybdate prior to the second hydrogen abstraction, and that the analogous N o-complex in ammoxidation undergoes two hydrogen abstractions to form acrylonitrile. Detailed reaction schemes are developed.
A rapid combustion unit (Baird and Tatlock) incorporating a combustion chamber provided with baffle plates for complete combustion of the sample without the use of a catalyst has been assembled in a glove box for the determination of carbon and hydrogen in actinide complexes. The unit has been modified employing a movable electric furnace and a proportional temperature controller, for decomposition of the sample at desired heating rates. The set-up was standardised employing various reference materials such as benzoic acid, acetanilide, sulphanilamide and 1-chloro 2:4 dinitrobenzene and the standard deviation in the measurements evaluated. It has also been used successfully for the determination of carbon in uranium carbide and carbon and hydrogen in some uranyl-#beta#-diketone-amine N-oxide complexes and in plutonium(IV) oxalate. (auth.).
A novel liquid phase alkylation of aniline with methanol over Zn/Cu salts modified kaolin assisted with a pair of porous carbon electrode in slurry-bed reactor under constant current intensity, room temperature and atmospheric pressure was reported. The Zn/Cu salts modified kaolin catalysts were synthesized and characterized by infrared spectrometer (IR), powder X-ray diffraction (XRD) and scanning electron microscopy (SEM), which showed that the transition metals were completely supported on kaolins structure and formed a pored one. The effect parameters, such as initial pH, electrolysis time, metal ratio with kaolin and salts composition in this electrochemical catalytic system, were studied. The procedure was inspected by ultraviolet-visible spectrum (UV-vis), and the product distributi...