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Production of Gasoline and Diesel from Biomass via Fast Pyrolysis, Hydrotreating and Hydrocracking: 2012 State of Technology and Projections to 2017

Description: This report summarizes the economic impact of the work performed at PNNL during FY12 to improve fast pyrolysis oil upgrading via hydrotreating. A comparison is made between the projected economic outcome and the actual results based on experimental data. Sustainability metrics are also included.
Date: August 27, 2013
Creator: Jones, Susanne B. & Snowden-Swan, Lesley J.
Partner: UNT Libraries Government Documents Department

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

Description: The purpose of this study is to evaluate a processing pathway for converting biomass into infrastructure-compatible hydrocarbon biofuels. This design case investigates production of fast pyrolysis oil from biomass and the upgrading of that bio-oil as a means for generating infrastructure-ready renewable gasoline and diesel fuels. This study has been conducted using similar methodology and underlying basis assumptions as the previous design cases for ethanol. The overall concept and specific processing steps were selected because significant data on this approach exists in the public literature. The analysis evaluates technology that has been demonstrated at the laboratory scale or is in early stages of commercialization. The fast pyrolysis of biomass is already at an early stage of commercialization, while upgrading bio-oil to transportation fuels has only been demonstrated in the laboratory and at small engineering development scale. Advanced methods of pyrolysis, which are under development, are not evaluated in this study. These may be the subject of subsequent analysis by OBP. The plant is designed to use 2000 dry metric tons/day of hybrid poplar wood chips to produce 76 million gallons/year of gasoline and diesel. The processing steps include: 1.Feed drying and size reduction 2.Fast pyrolysis to a highly oxygenated liquid product 3.Hydrotreating of the fast pyrolysis oil to a stable hydrocarbon oil with less than 2% oxygen 4.Hydrocracking of the heavy portion of the stable hydrocarbon oil 5.Distillation of the hydrotreated and hydrocracked oil into gasoline and diesel fuel blendstocks 6. Hydrogen production to support the hydrotreater reactors. The "as received" feedstock to the pyrolysis plant will be "reactor ready". This development will likely further decrease the cost of producing the fuel. An important sensitivity is the possibility of co-locating the plant with an existing refinery. In this case, the plant consists only of the first three steps: feed prep, ...
Date: February 25, 2009
Creator: Jones, Susanne B.; Valkenburt, Corinne; Walton, Christie W.; Elliott, Douglas C.; Holladay, Johnathan E.; Stevens, Don J. et al.
Partner: UNT Libraries Government Documents Department

Improvent of hydrogen solubility and entrainment in hydrocracker feedstocks. Quarterly report, April 1 - June 30, 1996

Description: The objective of this project is to determine the conditions for the hydrogen-heavy oil feed preparation so as to optimize the yield of hydrocracking reactions. Proper contacting of hydrogen with heavy oil on the catalytic bed is necessary to improve the yields of the hydrocracking reactions. It is most desirable to have the necessary amount of hydrogen available either in the dissolved or in entrained state, so that hydrogen diffusion to the reaction site does not provide rate controlling resistance to the overall rates of hydrocracking reactions. This project proposes to measure solubility and entrainment data for hydrogen in heavy oils at conditions such as in hydrocrackers, and investigate the improvement of these properties by usage of appropriate additives. Specifically, measurements will be carried out at temperatures up to 300{degrees} C and pressures up to 120 atmospheres. Correlations for solubility and entrainment kinetics will be developed from the measured data, and a method for estimating yield of hydrocracking reactions using these correlations will be suggested. Exxon Research and Engineering Company will serve as private sector collaborator providing A&T with test samples and some technical expertise that will assure successful completion of the project. The final experimental measurements for hydrogen solubility in hydrocarbons are in progress. The novel experimental apparatus has been successfully operated for these measurements. The calibration procedures and some of the initial data measurements are summarized.
Date: December 31, 1996
Creator: Kabadi, V.N.
Partner: UNT Libraries Government Documents Department

Improvement of hydrogen solubility and entrainment in hydrocracker feedstocks. Quarterly technical report, January 1, 1995--March 31, 1995

Description: The objective of this project is to determine the conditions for the hydrogen-heavy oil feed preparation so as to optimize the yield of hydrocracking reactions. Proper contacting of hydrogen with heavy oil on the catalytic bed is necessary to improve the yields of the hydrocracking reactions. It is most desirable to have the necessary amount of hydrogen available either in the dissolved or in entrained state, so that hydrogen diffusion to the reaction site does not provide rate controlling resistance to the overall rates of hydrocracking reactions. This project proposes to measure solubility and entrainment data for hydrogen in heavy oils at conditions such as in hydrocrackers, and investigate the improvement of these properties by usage of appropriate additives. Specifically, measurements will be carried out at temperatures up to 300{degrees}C and pressures up to 120 atmospheres. Correlations for solubility and entrainment kinetics will be developed from the measured data, and a method for estimating yield of hydrocracking reactions using these correlations will be suggested. Exxon Research and Engineering Company will serve as private sector collaborator providing A&T with test samples and some technical expertise that will assure successful completion of the project. Results are presented for solubility of hydrogen in hydrocarbons and in heavy petroleum fractions. Comparison with experimental data shows good agreements. It is also demonstrated that the model is easily applied to compute solubility of hydrogen in heavy petroleum fractions with fair degree of accuracy. Detailed results are presented.
Date: July 1, 1995
Creator: Kabadi, V.N.
Partner: UNT Libraries Government Documents Department

IMPROVED CATALYSTS FOR HEAVY OIL UPGRADING BASED ON ZEOLITE Y NANOPARTICLES ENCAPSULATED IN STABLE NANOPOROUS HOSTS

Description: The focus of this project is to improve the catalytic performance of zeolite Y for petroleum hydrocracking by synthesizing nanoparticles of the zeolite ({approx}20-25 nm) inside nanoporous silicate or aluminosilicate hosts. The encapsulated zeolite nanoparticles are expected to possess reduced diffusional path lengths, hence hydrocarbon substrates will diffuse in, are converted and the products quickly diffused out. This is expected to prevent over-reaction and the blocking of the zeolite pores and active sites will be minimized. In this phase of the project, procedures for the synthesis of ordered nanoporous silica, such as SBA-15, using block copolymers and nonionic surfactant were successful reproduced. Expansion of the pores sizes of the nanoporous silica using trimethylbenzene is suggested based on shift in the major X-Ray Diffraction peak in the products to lower 2 angles compared with the parent SBA-15 material. The synthesis of ordered nanoporous materials with aluminum incorporated in the predominantly silicate framework was attempted but is not yet successful, and the procedures needs will be repeated and modified as necessary. Nanoparticles of zeolite Y of particle sizes in the range 40 nm to 120 nm were synthesized in the presence of TMAOH as the particle size controlling additive.
Date: September 3, 2003
Creator: Ingram, Conrad
Partner: UNT Libraries Government Documents Department

A characterization and evaluation of coal liquefaction process streams. Quarterly technical progress report, January 1, 1996--March 31, 1996

Description: 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. This project builds on work performed in DOE Contract No. DE-AC22-89PC89883. Independent analyses by well-established methods are obtained of samples produced in direct coal liquefaction processes under evaluation by DOE. Additionally, analytical instruments and techniques which are currently under utilized for the purpose of examining coal-derived samples are being evaluated. The data obtained from this study is used to help guide current process development and to develop an improved data base on coal and coal liquids properties. A sample bank, established and maintained for use in this project, is available for use by other researchers. The reactivity of the non-distillable resids toward hydrocracking at liquefaction conditions (i.e., resid reactivity) is being examined. From the literature and data experimentally obtained, a mathematical kinetic model of resid conversion will be constructed. It is anticipated that such a model will provide insights useful for improving process performance and thus the economics of direct coal liquefaction.
Date: July 1, 1996
Creator: Robbins, G.A.; Brandes, S.D.; Winschel, R.A. & Burke, F.P.
Partner: UNT Libraries Government Documents Department

Electrocatalytic hydrocracking. Final report

Description: This report describes an electrocatalytic method for the chemical addition of hydrogen to a model hydrocarbon compound. In the method, hydrogen formed by water electrolysis at the counter electrode of an electrochemical cell is delivered via conduction through a proton-conducting solid electrolyte. The working electrode of the cell is, at the same time, a hydrocracking catalyst and therefore promotes the reaction of the hydrogen with the hydrocarbon. This process would have clear and distinct advantages over conventional hydroprocessing technologies in that the hydrogen concentration at the catalyst surface could be controlled and maintained by the applied electromotive force. This control would allow operation of the electrocatalytic reactor at ambient pressures instead of the extremely high hydrogen partial pressures required of conventional reactors. In addition, the direct delivery of hydrogen to the catalyst surface should inhibit coke formation and thus prolong the life of the catalyst. Finally, hydrogen utilization efficiencies should be greatly improved since the hydrogen is delivered directly to the reaction site thereby eliminating hydrogen solubility loss in the effluent stream. This report details the demonstration of (a) the ability of a solid electrolyte to perform as a catalyst, (b) the conduction of hydrogen through a solid electrolyte and (c) the simultaneous exploitation of these two properties. Hence, the essential concept of electrocatalytic hydrocracking has been demonstrated. An objective of future work in this area should be to determine whether the hydrocracking or hydrogenation reactions are actually enhanced during the electrocatalytic process when compared to the conventional catalytic process.
Date: June 1, 1992
Creator: Vaart, D.R. van der
Partner: UNT Libraries Government Documents Department

Improvement of hydrogen solubility and entrainment in hydrocracker feedstocks. Final technical report

Description: The project consisted of two tasks: (1) development of a thermodynamic model for hydrogen solubility in hydrocarbons and extension of this model to predict solubility of hydrogen in hydrocracker feedstocks at conditions similar to those of hydrocracking operations, and (2) design and construction of a gas solubility apparatus to measure solubility of hydrogen in hydrocarbons and in hydrocracker feedstocks. The theoretical work proposed was fully accomplished by developing a sophisticated model for hydrogen solubility in hydrocarbons and in hydrocracker feedstocks at advanced temperatures and pressures. The proposed experimental work ran into a number of obstacles, especially to get the original and newly designed on-line sampling technique to function properly. A number of calibrations and tests for reproducibility were necessary to assure the accuracy of measured data. Although a very well designed gas solubility apparatus was built, not much time was left to generate significant hydrogen solubility data. The plans are to use the apparatus in future to measure hydrogen solubility data in liquid fuels to facilitate more efficient design of fuel conversion systems.
Date: February 1, 1997
Creator: Kabadi, V.N.
Partner: UNT Libraries Government Documents Department

Novel bimetallic dispersed catalysts for temperature-programmed coal liquefaction. Quarterly technical progress report, July--September 1995

Description: Coal liquefaction involves cleavage of methylene, dimethylene and ether bridges connecting polycyclic aromatic units and the reactions of various oxygen functional groups. Here in this quarterly, we report on the hydrocracking of 4-(l-naphthylmethyl)bibenzyl in the presence of iron (Fe) catalysts and sulfur and residual wall catalytic effect. Catalytic hydrocracking of 4-(1-naphthylmethyl)bibenzyl (NMBB) predominantly yielded naphthalene and 4-methylbibenzyl. Various iron compounds were examined as catalyst precursors. Sulfur addition to most catalyst precursors led to substantially higher catalyst activity and higher conversion. NMBB was also treated with sulfur in the absence of iron compounds, in concentrations of 1.2-3.4 wt%, corresponding to the conditions present in reactions with added iron compounds. Increasing sulfur concentrations led to higher NMBB conversions. Furthermore, sulfur had a permanent effect on the reactor walls. A black sulfide layer formed on the surface which could not be removed mechanically. The supposed non-catalytic reactions done in the same reactor but after experiments with added sulfur showed higher conversions than comparable experiments done in new reactors. This wall catalytic effect can be reduced by treating the sulfided reactors with hydrochloric acid. The results of this work demonstrate the significant effect of sulfur addition and sulfur-induced residual wall effects on carbon-carbon bond cleavage and hydrogenation of aromatics.
Date: January 1, 1996
Creator: Song, Chunshan; Schmidt, E. & Schobert, H.H.
Partner: UNT Libraries Government Documents Department

Progress in the development and production of nanoscale iron-coating catalysts

Description: At the Pacific Northwest Laboratory (PNL) we have undertaken a program to investigate nanocrystalline ion-based powders as catalytic precursors in a variety of hydrocracking reactions, including coal liquefaction. One ultrafine powder synthesis method developed at PNL, the Rapid of precursors in Solution (RTDS) process, appears to be particularly large scale production of nanocrystalline powders. Using model compounds we have demonstrated that iron-based RTDS powders can be used to produce highly active carbon-carbon bond scission catalysts under reaction conditions relevant to coal liquefaction processes. In this paper we present recent results of attempts at modifying the activity of RTDS-generated iron-based catalyst powders by doping with other metals and the results of scaleup efforts to produce kilogram quantities of active catalyst precursor by this process.
Date: April 1, 1995
Creator: Matson, D.W.; Linehan, J.C.; Darab, J.G.; Watrob, H.M.; Lui, E.G.; Phelps, M.R. et al.
Partner: UNT Libraries Government Documents Department

IMPROVED CATALYSTS FOR HEAVY OIL UPGRADING BASED ON ZEOLITE Y NANOPARTICLES ENCAPSULATED IN STABLE NANOPOROUS HOSTS

Description: The focus of this project is to improve the catalytic performance of zeolite Y for heavy petroleum hydrocracking by synthesizing nanoparticles of the zeolite ({approx}20-30 nm) inside nanoporous silicate or aluminosilicate hosts of similar pore diameters. The encapsulated zeolite nanoparticles are expected to possess pores of reduced diffusional path lengths, hence hydrocarbon substrates will diffuse in, are converted and the products quickly diffused out. This is expected to prevent over-reaction, hence minimizing pore blockage and active sites deactivation. In this phase of the project, research activities were focused on refining procedures to: (a) improve the synthesis of ordered, high surface area nanoporous silica, such as SBA-15, with expanded pore size using trimethylbenzene as additive to the parent SBA-15 synthesis mixture; and (b) reduce the particle size of zeolite Y such that they can be effectively incorporated into the nanoporous silicas. The synthesis of high surface ordered nanoporous silica containing enlarged pores of diameter of 25 nm (larger than the standard size of 8.4 nm) using trimethylbenzene as a pore size expander was accomplished. The synthesis of zeolite Y nanoparticles with median pore size of approximately 50 nm (smaller than the 80 nm typically obtained with TMAOH) using combined TMABr/TMAOH as organic additives was also accomplished.
Date: June 30, 2004
Creator: Ingram, Conrad & Mitchell, Mark
Partner: UNT Libraries Government Documents Department

Hydrotreating process kinetics for bitumen and bitumen-derived liquids

Description: Hydrodenitrogenation, hydrodesulfurization and resid conversion data for the Whiterocks bitumen and bitumen-derived liquid were analyzed using a modified power rate law model. The model incorporated the space velocity and pressure since the plug flow equation may not be applicable to laboratory-scale reactors in which complete wetting of the catalyst may not be attained. The data were obtained with the reactor operating as a fixed bed reactor in the upflow mode. The space velocity (WHSV{sup {alpha}}) term was included to account for deviations from plug flow behavior. The exponents (a,p) and the kinetic parameters were obtained by combined non-linear regression and ODE solver techniques for the analysis of laboratory data. A simple nth order power rate law expression for hydrodenitrogenation and hydrodesulfurization was examined. The higher than first order kinetics for hydrodenitrogenation and hydrodesulfurization of the bitumen and bitumen-derived liquids were explained by invoking two parallel first-order reactions; one slow and the other fast. Parallel and consecutive reaction schemes were used to examine the extent of conversion of the resid fraction to middle distillate, gas oil and gasoline and the apparent kinetic parameters were determined. It was determined that the upflow operating mode was preferred to the trickle-bed mode in the laboratory reactor to insure plug flow behavior.
Date: March 1, 1993
Creator: Kwak, S.; Longstaff, D. C.; Deo, M. D. & Hanson, F. V.
Partner: UNT Libraries Government Documents Department

High conversion of coal to transportation fuels for the future with low HC gas production. Progress report No. 11, April 1--June 30, 1995

Description: The objectives of this research are: (1) produce a synthetic crude from coal at a cost lower than $30.00 per barrel; and (2) produce a fuel which is low in aromatics, yet of sufficiently high octane number for use in the gasoline-burning transportation vehicles of today. To meet this second objective, research was proposed, and funding awarded, for conversion of the highly-aromatic liquid product from coal conversion to a product high in isoparaffins, which compounds in the gasoline range exhibit a high octane number. Experimental coal liquefaction studies conducted in a batch microreactor in our laboratory have demonstrated potential for high conversions of coal to liquids with low yield of hydrocarbon (HC) gases, hence small consumption of hydrogen in the primary liquefaction step. Ratios of liquids/HC gases as high as 30/1, at liquid yields as high as 82% of the coal by weight, have been achieved. The principal objective of this work is to examine how nearly we may approach these results in a continuous-flow system, at a size sufficient to evaluate the process concept for production of transportation fuels from coal. A continuous-flow reactor system is to be designed, constructed and operated. The system is to be computer-operated for process control and data logging, and is to be fully instrumented. The primary liquid products will be characterized by GC, FTIR, and GC/MS, to determine the types and quantities of the principal components produced under conditions of high liquids production with high ratios of liquids/HC gases, hydrogen consumption for the conversion to primary liquids will be calculated. Conversion of the aromatics of this liquid product to isoparrafins will be investigated, to examine the potential for producing a transportation fuel from coal with satisfactory octane rating but low in aromatic content. Progress to date is described.
Date: July 1, 1995
Creator: Wiser, W.H. & Oblad, A.G.
Partner: UNT Libraries Government Documents Department

Direct liquefaction Proof-of-Concept Program, Hydrocarbon Technologies, Inc., Lawrenceville, New Jersey. Final topical report, Bench Run 02 (227-91)

Description: This report presents the results of Bench Run PB-02, conducted under the DOE Proof of Concept - Bench Option Program in direct coal liquefaction at Hydrocarbon Technologies, Inc. in Lawrenceville, New Jersey. Bench Run PB-02 was the second of the nine runs planned in the POC Bench Option Contract between the U.S. DOE and Hydrocarbon Technologies, Inc. The primary goal of this bench run was to evaluate the hybrid catalyst system, consisting of a dispersed slurry catalyst in one of the hydroconversion reactors and conventional supported extrudate catalyst in the other hydroconversion reactor, in a high-low two-stage temperature sequence, similar to the one operated at Wilsonville. This hybrid mode of operation with the high-low temperature sequence was studied during direct liquefaction of coal and in coprocessing of coal with Hondo resid and/or waste plastics under high space velocity operating conditions. Another important objective of Bench Run PB-02 was to investigate the novel {open_quotes}interstage internal recycle{close_quotes} of the second stage reactor slurry back to the first stage reactor. Other features of PB-02 included the use of an interstage separator and an in-line fixed bed hydrotreater. In general, it was found during Bench Run PB-02 that the {open_quote}hybrid type{close_quote} catalyst system was not effective for obtaining high levels of process performance as the {open_quote}all dispersed{close_quote} catalyst system, tested earlier, especially at high coal space velocities. The interstage internal recycle of second stage reactor slurry to the first stage reactor feed line was found to improve cracking of liquefaction products. The addition of small amounts of mixed plastics was found to improve the hydrogen utilization in both coal conversion and heavy oil hydrocracking reactions, i.e., plastics resulted in improving the overall distillate yield while at the same time reducing the light gas make and chemical hydrogen consumption.
Date: September 1, 1996
Creator: Comolli, A.G.; Pradhan, V.R.; Lee, T.L.K.; Karolkiewicz, W.F. & Popper, G.
Partner: UNT Libraries Government Documents Department

The extraction of bitumen from western oil sands: Volume 2. Final report

Description: The program is composed of 20 projects, of which 17 are laboratory bench or laboratory pilot scale processes or computer process simulations that are performed in existing facilities on the University of Utah campus in north-east Salt Lake City. These tasks are: (1) coupled fluidized-bed bitumen recovery and coked sand combustion; (2) water-based recovery of bitumen; (3) oil sand pyrolysis in a continuous rotary kiln reactor; (4) oil sand pyrolysis in a large diameter fluidized bed reactor; (5) oil sand pyrolysis in a small diameter fluidized bed reactor; (6) combustion of spent sand in a transport reactor; (7) recovery and upgrading of oil sand bitumen using solvent extraction methods; (8) fixed-bed hydrotreating of Uinta Basin bitumens and bitumen-derived hydrocarbon liquids; (9) ebullieted bed hydrotreating of bitumen and bitumen derived liquids; (10) bitumen upgrading by hydropyrolysis; (11) evaluation of Utah`s major oil sand deposits for the production of asphalt, high-energy jet fuels and other specialty products; (12) characterization of the bitumens and reservoir rocks from the Uinta Basin oil sand deposits; (13) bitumen upgrading pilot plant recommendations; (14) liquid-solid separation and fine tailings thickening; (15) in-situ production of heavy oil from Uinta Basin oil sand deposits; (16) oil sand research and development group analytical facility; and (17) process economics. This volume contains reports on nine of these projects, references, and a bibliography. 351 refs., 192 figs., 65 tabs.
Date: November 26, 1997
Creator: Oblad, A.G.; Dahlstrom, D.A.; Deo, M.D.; Fletcher, J.V.; Hanson, F.V.; Miller, J.D. et al.
Partner: UNT Libraries Government Documents Department

Production of ethanol from refinery waste gases. Phase 3. Engineering development. Annual report, April 1, 1995--May 15, 1996

Description: Refineries discharge large volumes of H2, CO, and CO 2 from cracking, coking, and hydrotreating operations. This R&D program seeks to develop, demonstrate, and commercialize a biological process for converting these waste gases into ethanol for blending with gasoline. A 200,000 BPD refinery could produce up to 38 million gallons ethanol per year. The program is being conducted in 3 phases: II, technology development; III, engineering development; and IV, demonstration. Phase I, exploratory development, has been completed. The research effort has yielded two strains (Isolates O-52 and C-01) which are to be used in the pilot studies to produce ethanol from CO, CO2, and H2 in petroleum waste gas. Results from single continuous stirred tank reactor (CSTR) laboratory tests have shown that 20-25 g/L ethanol can be produced with < 5 g/L acetic acid byproduct. Laboratory studies with two CSTRs in series have yielded ethanol concentrations of 30-35 g/L with 2-4 g/L acetic acid byproduct. Water recycle from distillation back to the fermenter shows that filtration of the water before distillation eliminates the recycle of toxic materials back to the fermenter. Product recovery in the process will use direct distillation to the azeotrope, followed by adsorption to produce neat ethanol. This is less energy intensive than e.g. solvent extraction, azeotropic distillation, or pervaporation. Economic projections are quite attractive; the economics are refinery stream dependent and thus vary depending on refinery location and operation.
Date: November 1, 1996
Creator: Arora, D.; Basu, R.; Phillips, J.R.; Wikstrom, C.V.; Clausen, E.C & Gaddy, J.L.
Partner: UNT Libraries Government Documents Department

Hydrocracking and hydroisomerization of long-chain alkanes and polyolefins over metal-promoted anion-modified transition metal oxides

Description: A method is described for cracking a feedstock by contacting the feedstock with a metal-promoted anion-modified metal oxide catalyst in the presence of hydrogen gas. The metal oxide of the catalyst is one or more of ZrO{sub 2}, HfO{sub 2}, TiO{sub 2} and SnO{sub 2}, and the feedstock is principally chains of at least 20 carbon atoms. The metal-promoted anion-modified metal oxide catalyst contains one or more of Pt, Ni, Pd, Rh, Ir, Ru, (Mn and Fe) or mixtures of them present between about 0.2% to about 15% by weight of the catalyst. The metal-promoted anion-modified metal oxide catalyst contains one or more of SO{sub 4}, WO{sub 3}, or mixtures of them present between about 0.5% to about 20% by weight of the catalyst.
Date: December 1996
Creator: Venkatesh, Koppampatti R.; Hu, Jianli; Tierney, John W. & Wender, Irving
Partner: UNT Libraries Government Documents Department

A characterization and evaluation of coal liquefaction process streams. The kinetics of coal liquefaction distillation resid conversion

Description: Under subcontract from CONSOL Inc., the University of Delaware studied the mechanism and kinetics of coal liquefaction resid conversion. The program at Delaware was conducted between August 15, 1994, and April 30, 1997. It consisted of two primary tasks. The first task was to develop an empirical test to measure the reactivity toward hydrocracking of coal-derived distillation resids. The second task was to formulate a computer model to represent the structure of the resids and a kinetic and mechanistic model of resid reactivity based on the structural representations. An introduction and Summary of the project authored by CONSOL and a report of the program findings authored by the University of Delaware researchers are presented here.
Date: March 1, 1998
Creator: Klein, M.T.; Calkins, W.H.; Huang, H.; Wang, S. & Campbell, D.
Partner: UNT Libraries Government Documents Department

Low severity upgrading of F-T waxes with solid superacids. Final report

Description: The use of solid acids, especially Pt/ZrO{sub 2}/SO{sub 4}, to convert long chain alkanes and Fischer-Tropsch waxes to liquid fuels under mild reaction conditions was explored in this work. Anion and/or hydrogenation metal modified zirconium oxides were synthesized, characterized, and tested for hydrocracking and hydroisomerization. of model compounds, chiefly with n-hexadecane. The relationship between catalytic activity and acidic character of the bifunctional Pt/ZrO{sub 2}/SO{sub 4} catalyst was investigated.
Date: September 30, 1995
Creator: Wender, I. & Tierney, J.W.
Partner: UNT Libraries Government Documents Department

Fine particle clay catalysts for coal liquefaction. Quarterly technical progress report, February 9, 1992--May 8, 1992

Description: An investigation of new methods for the production of iron-pillared clay catalysts and clay-supported iron hydroxyoxide catalysts and the determination of their catalytic activities was continued in this quarter. Previous work in this project showed that a catalyst prepared by adding ferric nitrate and ammonia to an acid-washed clay gave an active catalyst following sulfidation. Further testing of this catalyst with a model compound showed that its hydrocracking activity was considerably lower when used in 10% concentration rather than 50%. In contrast, the mixed iron/alumina pillared clay catalysts were still highly effective at 10% concentration and gave good conversions at one and two hour reaction times. An investigation of preparation methods demonstrated that calcination of both the iron hydroxyoxide-impregnated clay and the mixed iron/alumina pillared clays is essential for activity. High activity was obtained for these catalysts only when they were removed from the aqueous media rapidly, dried, and calcined. The use of ferric sulfate to prepare a clay-supported sulfated iron catalyst was attempted, the resulting catalyst was relatively inactive for hydrocracking. Several new catalysts were synthesized with the idea of decreasing the pillar density and thereby increasing the micropore volume. A zirconia-pillared clay with low pillar density was prepared and intercalated with triiron complex. The hydrocracking activity of this catalyst was somewhat lower than that of the mixed alumina/iron-pillared catalyst. Other new catalysts, that were prepared by first pillaring with an organic ammonium pillaring agent, then introducing a lower number of silica or alumina pillars, and finally the iron component, were also tested. The mixed alumina/iron-pillared catalysts was further tested at low concentration for pyrene hydrogenating and hydrocracking activities.
Date: October 1, 1995
Creator: Olson, E.S.
Partner: UNT Libraries Government Documents Department

Refining and end use study of coal liquids. Second quarter 1995 technical progress report, April--June 1995

Description: Bechtel, with Southwest Research Institute, Amoco Oil R&D, and the M.W. Kellogg Co. as subcontractors, initiated a study on November 1, 1993, for the U.S. Department of Energy`s (DOE`s) Pittsburgh Energy Technology Center (PETC) to determine the most cost effective and suitable combination of existing petroleum refinery processes needed to make specification transportation fuels or blending stocks, from direct and indirect coal liquefaction product liquids. This 47-month study, with an approved budget of $4.4 million dollars, is being performed under DOE Contract Number DE-AC22-93PC91029. A key objective is to determine the most desirable ways of integrating coal liquefaction liquids into existing petroleum refineries to produce transportation fuels meeting current and future, e.g. year 2000, Clean Air Act Amendment (CAAA) standards. An integral part of the above objectives is to test the fuels or blends produced and compare them with established ASTM fuels. The comparison will include engine tests to ascertain compliance of the fuels produced with CAAA and other applicable fuel quality and performance standards. The final part of the project includes a detailed economic evaluation of the cost of processing the coal liquids to their optimum products.
Date: December 1, 1995
Partner: UNT Libraries Government Documents Department

Novel bimetallic dispersed catalysts for temperature-programmed coal liquefaction. Technical progress report, October 1995--December 1995

Description: Coal liquefaction involves cleavage of methylene, dimethylene and ether bridges connecting polycyclic aromatic units and the reactions of various oxygen functional groups. Here in this quarterly, we report on the catalytic effects of several molybdenum-, cobalt-, and iron-containing compounds in the reactions of dibenzothiophene (DBT) with hydrogen under conditions related to coal liquefaction. The catalytic effects of several molybdenum-, cobalt-, and iron-containing compounds have been examined in the hydrogenation and hydrodesulfurization reactions of dibenzothiophene (DBT) under conditions related to coal liquefaction. The metal compounds are candidate catalyst precursors for direct coal liquefaction. The reactions were carried out in batch microautoclave reactors at 400{degrees}C for 30 minutes with 6.9 MPa (cold) hydrogen pressure, and tridecane solvent. A metal loading of 0.5 mol% resulted in low conversion and only hydrogenation. Addition of sulfur in 4:1 molar ratio led only to a minor increase in conversion and hydrodesulfurization. The use of a higher boiling solvent (octadecane vs. tridecane) was beneficial in providing increased conversion, hydrodesulfurization, and hydrogenation. An increase in metal compound loading to 36.2 mol% led to a dramatic increase in conversion, hydrodesulfurization, and hydrocracking. Molybdenum hexacarbonyl at 36 mol% loading, with added sulfur at 6:1 ratio and octadecane solvent, gave 100% conversion of dibenzothiophene to other products with 100% hydrodesulfurization. Ammonium tetrathiomolybdate and molybdenum(III) chloride are less active under similar conditions. A cobalt-molybdenum thiocubane complex gave unexpectedly low conversions. Iron and cobalt carbonyls also provided very low conversions, even with added sulfur.
Date: February 1, 1996
Creator: Song, C.; Cooke, W.S.; Schmidt, E. & Schobert, H.H.
Partner: UNT Libraries Government Documents Department

Fine particle clay catalysts for coal liquefaction. Quarterly technical progress report, May 9, 1992--August 8, 1992

Description: An investigation of new methods for the production of mixed pillared clay catalysts and clay-supported catalysts and determination of their catalytic activities were continued in this quarter. To demonstrate the reproducibility of the preparative method for high activity iron/alumina-pillared montmorillonite catalysts, a new batch of the catalyst was prepared and tested for hydrocracking activity with bibenzyl. This preparation gave conversion and product distribution similar to that reported previously. The mixed iron/alumina-pillared clay was also prepared using a pillaring solution that was aged for longer period of time. To determine the importance of the type of pillaring support in hydrocracking activity, iron/zirconia-pillared montmorillonite was prepared using the same technique as that for iron/alumina-pillared montmorillonite. The reaction of bibenzyl with the sulfided iron/zirconia-pillared catalyst gave a lower hydrocracking conversion than the iron/alumina-pillared catalyst. Addition of a second catalytic metal to the clay support was attempted to determine if a synergistic effect could improve liquefaction. Ferric nitrate and stannous chloride were added to the clay, but the resulting catalyst was relatively poor for hydrocracking and hydrogenation compared with ferric nitrate supported on the clay. New disposable iron catalysts with high acidity and surface area are desired for coal liquefaction. Synthetic iron aluminosilicates were prepared by methods similar to those used for the nickel-substituted synthetic mica montmorillonite (NiSMM) catalysts, which are very effective for hydrogenation and reforming of hydrocarbons. The iron aluminosilicate catalysts were tested for hydrocracking and hydrogenation of bibenzyl, naphthalene and pyrene. Pyrene hydrogenation was effectively catalyzed by the sulfided synthetic iron catalyst.
Date: October 1995
Creator: Olson, E. S.
Partner: UNT Libraries Government Documents Department

A characterization and evaluation of coal liquefaction process streams. Quarterly technical progress report, July 1--September 30, 1995

Description: 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, a mathematical kinetic model of resid conversion will be constructed. It is anticipated that such a model will provide insights useful for improving process performance and thus the economics of direct coal liquefaction. Some of the contract activities for this quarter are: We completed many of the analyses on the 81 samples received from HTI bench-scale run CMSL-9, in which coal, coal/mixed plastics, and coal/high density polyethylene were fed; Liquid chromatographic separations of the 15 samples in the University of Delaware sample set were completed; and WRI completed CP/MAS {sup 13}C-NMR analyses on the Delaware sample set.
Date: December 1, 1995
Creator: Robbins, G.A.; Brandes, S.D.; Winschel, R.A. & Burke, F.P.
Partner: UNT Libraries Government Documents Department