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Sample records for release direct coal liquefaction

  1. Design of generic coal conversion facilities: Process release---Direct coal liquefaction

    SciTech Connect

    Not Available

    1991-09-01

    The direct liquefaction portion of the PETC generic direct coal liquefaction process development unit (PDU) is being designed to provide maximum operating flexibility. The PDU design will permit catalytic and non-catalytic liquefaction concepts to be investigated at their proof-of-the-concept stages before any larger scale operations are attempted. The principal variations from concept to concept are reactor configurations and types. These include thermal reactor, ebullating bed reactor, slurry phase reactor and fixed bed reactor, as well as different types of catalyst. All of these operating modes are necessary to define and identify the optimum process conditions and configurations for determining improved economical liquefaction technology.

  2. Reaction engineering in direct coal liquefaction

    NASA Astrophysics Data System (ADS)

    Shah, Y. T.

    Processes for direct coal liquefaction by solvent extraction are considered along with the structure and properties of coal and the mechanism of coal liquefaction, heteroatom removal during liquefaction, kinetic models for donor-solvent coal liquefaction, the design of coal liquefaction reactors, and the refining of coal liquids. Attention is given to the catalytic hydrogenation of coal in the presence of a solvent, the origin and character of coal, laboratory reactors for rate measurements, reaction networks based on lumped fractions, free-radical reaction models, reactor types, the compatibility of coal-derived liquids and petroleum fuels, the stability of coal liquids, thermal cracking, catalytic hydrotreating, catalytic cracking, and catalytic reforming.

  3. Direct coal liquefaction process

    DOEpatents

    Rindt, J.R.; Hetland, M.D.

    1993-10-26

    An improved multistep liquefaction process for organic carbonaceous mater which produces a virtually completely solvent-soluble carbonaceous liquid product. The solubilized product may be more amenable to further processing than liquid products produced by current methods. In the initial processing step, the finely divided organic carbonaceous material is treated with a hydrocarbonaceous pasting solvent containing from 10% and 100% by weight process-derived phenolic species at a temperature within the range of 300 C to 400 C for typically from 2 minutes to 120 minutes in the presence of a carbon monoxide reductant and an optional hydrogen sulfide reaction promoter in an amount ranging from 0 to 10% by weight of the moisture- and ash-free organic carbonaceous material fed to the system. As a result, hydrogen is generated via the water/gas shift reaction at a rate necessary to prevent condensation reactions. In a second step, the reaction product of the first step is hydrogenated.

  4. Direct coal liquefaction process

    DOEpatents

    Rindt, John R.; Hetland, Melanie D.

    1993-01-01

    An improved multistep liquefaction process for organic carbonaceous mater which produces a virtually completely solvent-soluble carbonaceous liquid product. The solubilized product may be more amenable to further processing than liquid products produced by current methods. In the initial processing step, the finely divided organic carbonaceous material is treated with a hydrocarbonaceous pasting solvent containing from 10% and 100% by weight process-derived phenolic species at a temperature within the range of 300.degree. C. to 400.degree. C. for typically from 2 minutes to 120 minutes in the presence of a carbon monoxide reductant and an optional hydrogen sulfide reaction promoter in an amount ranging from 0 to 10% by weight of the moisture- and ash-free organic carbonaceous material fed to the system. As a result, hydrogen is generated via the water/gas shift reaction at a rate necessary to prevent condensation reactions. In a second step, the reaction product of the first step is hydrogenated.

  5. Advanced direct coal liquefaction concepts - appendix

    SciTech Connect

    Berger, D.J.; Parker, R.J.; Simpson, P.L.

    1994-07-01

    This detailed appendix presents the results of direct coal liquefaction studies performed by the contractor. Several hundred tables summarizing the chemical compostion for runs of a bench scale reactor are presented.

  6. Advanced progress concepts for direct coal liquefaction

    SciTech Connect

    Anderson, R.; Derbyshire, F.; Givens, E.

    1995-09-01

    Given the low cost of petroleum crude, direct coal liquefaction is still not an economically viable process. The DOE objectives are to further reduce the cost of coal liquefaction to a more competitive level. In this project the primary focus is on the use of low-rank coal feedstocks. A particular strength is the use of process-derived liquids rather than model compound solvents. The original concepts are illustrated in Figure 1, where they are shown on a schematic of the Wilsonville pilot plant operation. Wilsonville operating data have been used to define a base case scenario using run {number_sign}263J, and Wilsonville process materials have been used in experimental work. The CAER has investigated: low severity CO pretreatment of coal for oxygen rejection, increasing coal reactivity and mg inhibiting the propensity for regressive reactions; the application of more active. Low-cost Fe and Mo dispersed catalysts; and the possible use of fluid coking for solids rejection and to generate an overhead product for recycle. CONSOL has investigated: oil agglomeration for coal ash rejection, for the possible rejection of ash in the recycled resid, and for catalyst addition and recovery; and distillate dewaxing to remove naphthenes and paraffins, and to generate an improved quality feed for recycle distillate hydrogenation. At Sandia, research has been concerned with the production of active hydrogen donor distillate solvent fractions produced by the hydrogenation of dewaxed distillates and by fluid coking via low severity reaction with H{sub 2}/CO/H{sub 2}O mixtures using hydrous metal oxide and other catalysts.

  7. Coal liquefaction

    DOEpatents

    Schindler, Harvey D.

    1985-01-01

    In a two-stage liquefaction wherein coal, hydrogen and liquefaction solvent are contacted in a first thermal liquefaction zone, followed by recovery of an essentially ash free liquid and a pumpable stream of insoluble material, which includes 850.degree. F.+ liquid, with the essentially ash free liquid then being further upgraded in a second liquefaction zone, the liquefaction solvent for the first stage includes the pumpable stream of insoluble material from the first liquefaction stage, and 850.degree. F.+ liquid from the second liquefaction stage.

  8. Case studies on direct liquefaction of low rank Wyoming coal

    SciTech Connect

    Adler, P.; Kramer, S.J.; Poddar, S.K.

    1995-12-31

    Previous Studies have developed process designs, costs, and economics for the direct liquefaction of Illinois No. 6 and Wyoming Black Thunder coals at mine-mouth plants. This investigation concerns two case studies related to the liquefaction of Wyoming Black Thunder coal. The first study showed that reducing the coal liquefaction reactor design pressure from 3300 to 1000 psig could reduce the crude oil equivalent price by 2.1 $/bbl provided equivalent performing catalysts can be developed. The second one showed that incentives may exist for locating a facility that liquifies Wyoming coal on the Gulf Coast because of lower construction costs and higher labor productivity. These incentives are dependent upon the relative values of the cost of shipping the coal to the Gulf Coast and the increased product revenues that may be obtained by distributing the liquid products among several nearby refineries.

  9. Recent progress in the direct liquefaction of coal.

    PubMed

    Lumpkin, R E

    1988-02-19

    Interest in direct coal liquefaction steadily decreased during the 1980s as the price of crude oil dropped; there is now only one integrated coal liquefaction pilot plant active full time in the United States. The economics derived early in the decade established the price of transportation fuels from coal at $80 per barrel or higher. However, there have been dramatic improvements in the technology since 1983 that have not been widely appreciated. Recent designs and cost estimates show that a 60 percent decrease in the cost of liquid fuels from coal to an equivalent of $35 per barrel for crude oil. Although this cost is not low enough to justify immediate commercialization, additional improvements have been identified that could make direct liquefaction an attractive way to produce gasoline and other conventional fuels. PMID:17759033

  10. STUDY OF SOLVENT AND CATALYST INTERACTIONS IN DIRECT COAL LIQUEFACTION

    SciTech Connect

    Michael T. Klein

    2000-01-01

    Using a reactor in which the coal is physically separated from the solid catalyst by a porous wall permeable to the hydrogen donor solvent, it was shown that direct contact between the catalyst and the coal is not required for catalyzed coal liquefaction. This occurs however only when there is a hydrogen atmosphere, as liquefaction with catalyst participation does not occur in a nitrogen atmosphere. Liquefaction by hydrogen transfer from the donor solvent itself does occur. This suggests that there is transfer of hydrogen from the catalyst to the coal via the solvent. The character of the solvent makes a significant difference, the better solvents being good hydrogen donors. These results indicate that the role of the catalyst may be to regenerate the spent hydrogen donor solvent during the liquefaction process. The peak temperature for volatiles evolution has been shown to be a reproducible measure of the coal rank. This was shown by an excellent correlation (R2 = 0.998) between peak volatiles temperatures (by TGA) and vitrinite reflectance. Using TG/MS, the volatiles contents of coals of a wide range of ranks was determined. The low rank coals emit largely phenols and some other oxygen compounds and olefins. The higher rank coals emit largely aromatic hydrocarbons and some olefins.

  11. The application of advanced analytical techniques to direct coal liquefaction

    SciTech Connect

    Brandes, S.D.; Winschel, R.A.; Burke, F.P.; Robbins, G.A.

    1991-12-31

    Consol is coordinating a program designed to bridge the gap between the advanced, modern techniques of the analytical chemist and the application of those techniques by the direct coal liquefaction process developer, and to advance our knowledge of the process chemistry of direct coal liquefaction. The program is designed to provide well-documented samples to researchers who are utilizing techniques potentially useful for the analysis of coal derived samples. The choice of samples and techniques was based on an extensive survey made by Consol of the present status of analytical methodology associated with direct coal liquefaction technology. Sources of information included process developers and analytical chemists. Identified in the survey are a number of broadly characterizable needs. These categories include a need for: A better understanding of the nature of the high molecular weight, non-distillable residual materials (both soluble and insoluble) in the process streams; improved techniques for molecular characterization, heteroatom and hydrogen speciation and a knowledge of the hydrocarbon structural changes across coal liquefaction systems; better methods for sample separation; application of advanced data analysis methods; the use of more advanced predictive models; on-line analytical techniques; and better methods for catalyst monitoring.

  12. Direct liquefaction of plastics and coprocessing of coal with plastics

    SciTech Connect

    Huffman, G.P.; Feng, Z.; Mahajan, V.

    1995-12-31

    The objectives of this work were to optimize reaction conditions for the direct liquefaction of waste plastics and the coprocessing of coal with waste plastics. In previous work, the direct liquefaction of medium and high density polyethylene (PE), polypropylene (PPE), poly(ethylene terephthalate) (PET), and a mixed plastic waste, and the coliquefaction of these plastics with coals of three different ranks was studied. The results established that a solid acid catalyst (HZSM-5 zeolite) was highly active for the liquefaction of the plastics alone, typically giving oil yields of 80-95% and total conversions of 90-100% at temperatures of 430-450 {degrees}C. In the coliquefaction experiments, 50:50 mixtures of plastic and coal were used with a tetralin solvent (tetralin:solid = 3:2). Using approximately 1% of the HZSM-5 catalyst and a nanoscale iron catalyst, oil yields of 50-70% and total conversion of 80-90% were typical. In the current year, further investigations were conducted of the liquefaction of PE, PPE, and a commingled waste plastic obtained from the American Plastics Council (APC), and the coprocessing of PE, PPE and the APC plastic with Black Thunder subbituminous coal. Several different catalysts were used in these studies.

  13. Direct use of methane in coal liquefaction

    DOEpatents

    Sundaram, Muthu S.; Steinberg, Meyer

    1987-01-01

    This invention relates to a process for converting solid carbonaceous material, such as coal, to liquid and gaseous hydrocarbons utilizing methane, generally at a residence time of about 20-120 minutes at a temperature of 250.degree.-750.degree. C., preferably 350.degree.-450.degree. C., pressurized up to 6000 psi, and preferably in the 1000-2500 psi range, preferably directly utilizing methane 50-100% by volume in a mix of methane and hydrogen. A hydrogen donor solvent or liquid vehicle such as tetralin, tetrahydroquinoline, piperidine, and pyrolidine may be used in a slurry mix where the solvent feed is 0-100% by weight of the coal or carbonaceous feed. Carbonaceous feed material can either be natural, such as coal, wood, oil shale, petroleum, tar sands, etc., or man-made residual oils, tars, and heavy hydrocarbon residues from other processing systems.

  14. Direct use of methane in coal liquefaction

    DOEpatents

    Sundaram, M.S.; Steinberg, M.

    1985-06-19

    This invention relates to a process for converting solid carbonaceous material, such as coal, to liquid and gaseous hydrocarbons utilizing methane, generally at a residence time of about 20 to 120 minutes at a temperature of 250 to 750/sup 0/C, preferably 350 to 450/sup 0/C, pressurized up to 6000 psi, and preferably in the 1000 to 2500 psi range, preferably directly utilizing methane 50 to 100% by volume in a mix of methane and hydrogen. A hydrogen donor solvent or liquid vehicle such as tetralin, tetrahydroquinoline, piperidine, and pyrolidine may be used in a slurry mix where the solvent feed is 0 to 100% by weight of the coal or carbonaceous feed. Carbonaceous feed material can either be natural, such as coal, wood, oil shale, petroleum, tar sands, etc., or man-made residual oils, tars, and heavy hydrocarbon residues from other processing systems. 1 fig.

  15. Some thoughts on the strategy of direct coal liquefaction -- Partial liquefaction and utilization of heavy liquefaction products

    SciTech Connect

    Liu, Z.; Yang, J.

    1998-12-31

    Hydrogenation has long been the only goal of coal liquefaction. However, analysis show that partial hydrogenation along with carbon rejection may be a better strategy for coal liquefaction, which reduces hydrogen consumption and reaction severity, eliminates the necessity for expensive catalyst, and may results in better economy for overall liquefaction. The hydrogenation and carbon rejection approach can be called partial liquefaction of coal. This paper presents analysis supporting the strategy of partial coal liquefaction based on the point of view of mass and energy balance, chemical reaction kinetics, reactivity of coal constituents and possible use of the heavy liquefaction products.

  16. STUDY OF SOLVENT AND CATALYST INTERACTIONS IN DIRECT COAL LIQUEFACTION

    SciTech Connect

    Michael T. Klein; William H. Calkins; Jasna Tomic

    2000-10-04

    To provide a better understanding of the roles of a solid catalyst and the solvent in Direct Coal Liquefaction, a small reactor was equipped with a porous-walled basket which was permeable to the solvent but was not permeable to the coal or solid catalyst. With this equipment and a high volatile bituminous coal it was found that direct contact between the catalyst in the basket and the coal outside the basket is not required for catalyzed coal liquefaction. The character of the solvent in this system makes a significant difference in the conversion of the coal, the better solvents being strong donor solvents. Because of the extensive use of thermogravimetric analysis in this laboratory, it was noted that the peak temperature for volatiles evolution from coal was a reliable measure of coal rank. Because of this observation, a variety of coals of a range of ranks was investigated. It was shown in this work that measuring the peak temperature for volatiles evolution was a quite precise indicator of rank and correlated closely with the rank value obtained by measuring vitrinite reflectance, a more difficult measurement to make. This prompted the desire to know the composition of the volatile material evolved as a function of coal rank. This was then measured by coupling a TGA to a mass spectrometer using laser activation and photoionization detection TG-PI-MS. The predominant species in volatiles of low rank coal turned out to be phenols with some alkenes. As the rank increases, the relative amounts of alkene and aromatic hydrocarbons increases and the oxygenated species decrease. It was shown that these volatiles were actually pyrolytic products and not volatilization products of the coal. Solvent extraction experiments coupled with Thermogravimetric-photoionization-mass spectrometry (TG-PI-MS) indicated that the low boiling and more extractable material are essentially similar in chemical types to the non-extractable portions but apparently higher molecular weight

  17. Short Contact Time Direct Coal Liquefaction Using a Novel Batch Reactor

    SciTech Connect

    He Huang; Michael T. Klein; William H. Calkins

    1997-01-30

    The primary objective of this research is to optimize the design and operation of the bench scale batch reactor (SCTBR) for studying direct coal liquefaction at short contact times (.01 to 10 minutes or longer). Additional objectives are to study the kinetics of direct coal liquefaction particularly at short reaction times and to investigate the role of organic oxygen components of coal and their reaction pathways during coal liquefaction. Many of those objectives have already been achieved. This quarterly report discusses further kinetic studies of the liquefaction in tetralin of a Montana Lignite, Wyodak-Anderson subbituminous coal, Illinois #6 hv bituminous coal, Pittsburgh #8 hv bituminous coals, and Pocohontas lV bituminous coal at short contact times. All of these coals showed a distinct extraction stage. Further work has also been done to attempt to clarify the role of the liquefaction solvent in the direct liquefaction process.

  18. Subtask 3.9 - Direct Coal Liquefaction Process Development

    SciTech Connect

    Aulich, Ted; Sharma, Ramesh

    2012-07-01

    The Energy and Environmental Research Center (EERC), in partnership with the U.S. Department of Energy (DOE) and Accelergy Corporation, an advanced fuels developer with technologies exclusively licensed from ExxonMobil, undertook Subtask 3.9 to design, build, and preliminarily operate a bench-scale direct coal liquefaction (DCL) system capable of converting 45 pounds/hour of pulverized, dried coal to a liquid suitable for upgrading to fuels and/or chemicals. Fabrication and installation of the DCL system and an accompanying distillation system for off-line fractionation of raw coal liquids into 1) a naphtha middle distillate stream for upgrading and 2) a recycle stream was completed in May 2012. Shakedown of the system was initiated in July 2012. In addition to completing fabrication of the DCL system, the project also produced a 500-milliliter sample of jet fuel derived in part from direct liquefaction of Illinois No. 6 coal, and submitted the sample to the Air Force Research Laboratory (AFRL) at Wright Patterson Air Force Base, Dayton, Ohio, for evaluation. The sample was confirmed by AFRL to be in compliance with all U.S. Air Force-prescribed alternative aviation fuel initial screening criteria.

  19. Status of health and environmental research relative to direct coal liquefaction: 1976 to the present

    SciTech Connect

    Gray, R.H.; Cowser, K.E.

    1982-06-01

    This document describes the status of health and environmental research efforts, supported by the US Department of Energy (DOE), to assist in the development of environmentally acceptable coal liquefaction processes. Four major direct coal liquefaction processes are currently in (or have been investigated at) the pilot plant stage of development. Two solvent refined coal processes (SRC-I and -II), H-coal (a catalytic liquefaction process) and Exxon donor solvent (EDS). The Pacific Northwest Laboratory was assigned responsibility for evaluating SRC process materials and prepared comprehensive health and environmental effects research program plans for SRC-I and -II. A similar program plan was prepared for H-coal process materials by the Oak Ridge National Laboratory. A program has been developed for EDS process materials by Exxon Research and Engineering Co. The program includes short-term screening of coal-derived materials for potential health and ecological effects. Longer-term assays are used to evaluate materials considered most representative of potential commercial practice and with greatest potential for human exposure or release to the environment. Effects of process modification, control technologies and changing operational conditions on potential health and ecological effects are also being evaluated. These assessments are being conducted to assist in formulating cost-effective environmental research programs and to estimate health and environmental risks associated with a large-scale coal liquefaction industry. Significant results of DOE's health and environmental research efforts relative to coal liquefaction include the following: chemical characterization, health effects, ecological fate and effects, amelioration and risk assessment.

  20. Short Contact Time Direct Coal Liquefaction Using a Novel Batch Reactor

    SciTech Connect

    He Huang; Michael T. Klein; William H. Calkins

    1997-04-03

    The primary objective of this research is to optimize the design and operation of the bench scale batch reactor (SCTBR) for studying direct coal liquefaction at short contact times (.01 to 10 minutes or longer) . An additional objective is to study the kinetics of direct coal liquefaction particularly at short reaction times. Both of these objectives have been nearly achieved, however this work has shown the great importance of the liquefaction solvent characteristics and the solvent-catalyst interaction on the liquefaction process. This has prompted us to do a preliminary investigation of solvents and the solvent-catalyst systems in coal liquefaction. SUMMARY AND CONCLUSIONS 1) Conversion vs time data have been extended to 5 coals of ranks from lignite to low volatile bituminous coal. A broad range of reaction rates have been observed with a maximum in the high volatile bituminous range. 2) A series of direct coal liquefaction runs have been made using a range of nitrogen containing solvents that given high liquefaction conversions of coal. These runs are now being analyzed. 3) The coalification process has been shown by TGA to go through an intermediate stage which may account for the greater reactivity of bituminous coals in the direct coal liquefaction process. 4) It was shown that coal rank can be accurately determined by thermogravimetric analysis

  1. Cooperative research program in coal liquefaction

    SciTech Connect

    Huffman, G.P.; Sendlein, L.V.A.

    1991-01-01

    This report is a coordinated effort of the Consortium for Fossil Fuel Liquefaction Science. The topics concerning coal liquefaction discussed are: sulfate promoted metal oxides as direct coal liquefaction catalysts; low temperature depolymerization and liquefaction of premium R.S. coal samples; construction of continuous flow-through gas reactor for liquefaction investigations; generic structural characterization and liquefaction research; macerals, model compounds and iron catalyst dispersion; coal structure/liquefaction yield correlation by means of advanced NMR techniques; GC/MS of model compound mixtures; catalytic cracking, hydrogenation and liquefaction of coals under milder conditions; ENDOR investigations of coal liquefaction under mild conditions; catalytic dehydrogenation of model compounds in relation to direct coal liquefaction; surface characterization of catalyst added coal samples; computational chemistry of model compounds and molecular fragments of relevance to coal liquefaction; chemical characterization and hydrogenation reactions of single coal particles; thermolytic cleavage of selected coal-related linkages at mild temperatures; solvent sorption and FTIR studies on the effect of catalytic depolymerization reactions in coal; bioprocessing of coal; chemical routes to breaking bonds; novel liquefaction concepts cyclic olefins: novel new donors for coal liquefaction; better hydrogen transfer in coal liquefaction; catalytic hydropyrolysis and energized extraction of coals; gallium catalyst in mild coal liquefaction; potential of temperature microscope in coal liquefaction; evaluation of nitride catalysts for hydrotreatment and coal liquefaction; coprocessing and coal liquefaction with novel catalysts.

  2. Cooperative research program in coal liquefaction

    SciTech Connect

    Huffman, G.P.; Sendlein, L.V.A.

    1990-01-01

    Cooperative research in coal liquefaction is presented. Topics include: Sulfate-promoted metal oxides as direct coal liquefaction catalysts; low temperature depolymerization and liquefaction of premium US coal samples; construction of continuous flow-through gas reactor for liquefaction investigations; examination of ferric sulfide as a liquefaction catalyst; generic structural characterization and liquefaction research; spectroscopic studies of coal macerals depolymerization catalyzed by iron chloride; characterization of catalysts used in coal hydrogenation systems; coal structure/liquefaction yield correlation by means of advanced NMR techniques; mass spectrometry of coal derived liquids: determination of molecular weight distributions; catalyst cracking, hydrogenation and liquefaction of coals under milder conditions; ENDOR investigations of coal liquefaction under mild conditions; direct determination of hydroaromatic structures in coal and coal conversion products by catalytic dehydrogenation; surface characterization of APCSB coals by XPS; computation chemistry of model compounds and molecular fragments of relevance to coal liquefaction; chemical characterization and hydrogenation reactions of single coal particles; the role of hydrogen during liquefaction using donor and non-donor solvents; solvent sorption and FTIR studies on the effect of catalytic depolymerization reactions in coal; bioprocessing of coal; chemical routes to breaking bonds: new approaches to low-temperature liquefaction; an investigation into the reactivity of isotetralin and tetralin using molecular orbital calculations; coal liquefaction modification for enhanced reactivity; catalytic hydropyrolysis and energized extraction of coals; gallium catalyst in mild coal liquefaction -- potential of temperature microscope in coal liquefaction; evaluation of nitride catalysts for hydrotreatment and coal liquefaction; and improved catalysts for coal liquefaction and coprocessing.

  3. Use of ultrasound for enhanced direct coal liquefaction

    SciTech Connect

    Bendale, P.G. ); Tierney, J.W.; Wender, I. . Dept. of Chemical and Petroleum Engineering)

    1989-01-01

    The objective of this project is to investigate whether high- intensity ultrasound is capable of inducing coal liquefaction under mild conditions of temperature and pressure in the presence of a solvent and in the presence or absence of a liquefaction catalyst. The role of high-intensity ultrasound in effective dispersion of solids and/or activation of catalyst will also be investigated using an appropriate liquefaction catalyst. The study is being conducted in two parts. In the first part, model compounds are being subjected to high-intensity ultrasound to determine if any chemical bonds are broken under the action of ultrasound. In the second part of the study, the effect of ultrasound on both catalyzed and noncatalyzed coal liquefaction will be determined. Two coals (sub-bituminous and bituminous) will be studied using an appropriate hydrogen donor solvent and molybdenum sulfide as catalyst. 4 refs., 2 tabs.

  4. Novel use of residue from direct coal liquefaction process

    SciTech Connect

    Jianli Yang; Zhaixia Wang; Zhenyu Liu; Yuzhen Zhang

    2009-09-15

    Direct coal liquefaction residue (DCLR) is, commonly, designed to be used as a feed stock for gasification or combustion. Use of DCLR as a value added product is very important for improving overall economy of direct coal liquefaction processes. This study shows that the DCLR may be used as a pavement asphalt modifier. The modification ability is similar to that of Trinidad Lake Asphalt (TLA), a superior commercial modifier. Asphalts modified by two DCLRs meet the specifications of ASTM D5710 and BSI BS-3690 designated for the TLA-modified asphalts. The required addition amount for the DCLRs tested is less than that for TLA due possibly to the high content of asphaltene in DCLRs. Different compatibility was observed for the asphalts with the same penetration grade but from the different origin. Different components in the DCLR play different roles in the modification. Positive synergetic effects among the fractions were observed, which may due to the formation of the stable colloid structure. Unlike polymer-type modifier, the structure of asphalt-type modifier has a similarity with petroleum asphalts which favors the formation of a stable dispersed polar fluid (DPF) colloid structure and improves the performance of pavement asphalt. 12 refs., 1 fig., 6 tabs.

  5. SHORT CONTACT TIME DIRECT COAL LIQUEFACTION USING A NOVEL BATCH REACTOR

    SciTech Connect

    Michael T. Klein; William H. Calkins

    1997-10-29

    The overall goal of this research is to develop an understanding of the Direct Coal Liquefaction process at the molecular level. Many approaches have been used to study this process including kinetic studies, study of the liquefaction products, study of the effect of reaction variables, such as temperature, solvent type and composition, the changing nature and composition of the coal during liquefaction, and the distribution in the liquefaction products of the hydrogen consumed. While all these studies have contributed to our growing knowledge of the liquefaction process, an adequate understanding of direct liquefaction still eludes us. This is due to many reasons including: the complexity and variable nature of coal itself and the many different chemical reactions which are occurring simultaneously during direct coal liquefaction. We believe that a study of the liquefaction process at the very early stages will avoid the complexities of secondary reactions associated with free radical high temperature processes that are clearly involved in direct coal liquefaction. This prompted us to devise a reactor system which avoids long heat up and cool-down times associated with previous kinetic studies, and allows kinetic measurements even at as short as the first few seconds of the liquefaction reaction.

  6. Continuous bench-scale slurry catalyst testing direct coal liquefaction rawhide sub-bituminous coal

    SciTech Connect

    Bauman, R.F.; Coless, L.A.; Davis, S.M.

    1995-12-31

    In 1992, the Department of Energy (DOE) sponsored research to demonstrate a dispersed catalyst system using a combination of molybdenum and iron precursors for direct coal liquefaction. This dispersed catalyst system was successfully demonstrated using Black Thunder sub-bituminous coal at Wilsonville, Alabama by Southern Electric International, Inc. The DOE sponsored research continues at Exxon Research and Development Laboratories (ERDL). A six month continuous bench-scale program using ERDL`s Recycle Coal Liquefaction Unit (RCLU) is planned, three months in 1994 and three months in 1995. The initial conditions in RCLU reflect experience gained from the Wilsonville facility in their Test Run 263. Rawhide sub-bituminous coal which is similar to the Black Thunder coal tested at Wilsonville was used as the feed coal. A slate of five dispersed catalysts for direct coal liquefaction of Rawhide sub-bituminous coal has been tested. Throughout the experiments, the molybdenum addition rate was held constant at 100 wppm while the iron oxide addition rate was varied from 0.25 to 1.0 weight percent (dry coal basis). This report covers the 1994 operations and accomplishments.

  7. STUDY OF SOLVENT AND CATALYST INTERACTIONS IN DIRECT COAL LIQUEFACTION

    SciTech Connect

    Michael T. Klein

    1998-10-01

    Major objectives of the present project are to develop a better understanding of the roles of the catalyst and the liquefaction solvent in the coal liquefaction process. An open question concerning the role of the catalyst is whether intimate contact between the catalyst and the coal particles is important or required. To answer this question, it had been planned to coat an active catalyst with a porous silica coating which was found to retain catalyst activity while preventing actual contact between catalyst and coal. Consultation with people in DuPont who coat catalysts for increasing abrasion resistance have indicated that only portions of the catalyst are coated by their process (spray drying) and that sections of uncoated catalyst remain. For that reason, it was decided to suspend the catalyst in a basket separated from the coal in the reactor. The basket walls were to be permeable to the liquefaction solvent but not to the coal particles. Several such baskets were constructed of stainless steel with holes which would not permit passage of coal particles larger than 30 mesh. Liquefactions run with the coal of greater than 30 mesh size gave normal conversion of coal to liquid in the absence of catalyst in the basket, but substantially increased conversion when Ni/Mo on alumina catalyst was in the basket. While this result is interesting and suggestive of some kind of mass transfer of soluble material occurring between the catalyst and the coal, it does not eliminate the possibility of breakdown of the coal particle into particle sizes permeable to the basket. Indeed, a small amount of fine coal has been found inside the basket. To determine whether fine coal from breakdown of the coal particles is responsible for the conversion, a new basket is being prepared with 0.5{micro}m pore size.

  8. Direct coal liquefaction baseline design and system analysis

    SciTech Connect

    Not Available

    1991-04-01

    The primary objective of the study is to develop a computer model for a base line direct coal liquefaction design based on two stage direct coupled catalytic reactors. This primary objective is to be accomplished by completing the following: a base line design based on previous DOE/PETC results from Wilsonville pilot plant and other engineering evaluations; a cost estimate and economic analysis; a computer model incorporating the above two steps over a wide range of capacities and selected process alternatives; a comprehensive training program for DOE/PETC Staff to understand and use the computer model; a thorough documentation of all underlying assumptions for baseline economics; and a user manual and training material which will facilitate updating of the model in the future.

  9. Direct coal liquefaction baseline design and system analysis

    SciTech Connect

    Not Available

    1991-07-01

    The primary objective of the study is to develop a computer model for a base line direct coal liquefaction design based on two stage direct coupled catalytic reactors. This primary objective is to be accomplished by completing the following: a base line design based on previous DOE/PETC results from Wilsonville pilot plant and other engineering evaluations; a cost estimate and economic analysis; a computer model incorporating the above two steps over a wide range of capacities and selected process alternatives; a comprehensive training program for DOE/PETC Staff to understand and use the computer model; a thorough documentation of all underlying assumptions for baseline economics; and a user manual and training material which will facilitate updating of the model in the future.

  10. Direct coal liquefaction baseline design and system analysis

    SciTech Connect

    Not Available

    1991-01-01

    The primary objective of the study is to develop a computer model for a base line direct coal liquefaction design based on two stage direct coupled catalytic reactors. This primary objective is to be accomplished by completing the following: a base line design based on previous DOE/PETC results from Wilsonville pilot plant and other engineering evaluations; a cost estimate and economic analysis; a computer model incorporating the above two steps over a wide range of capacities and selected process alternatives; a comprehensive training program for DOE/PETC Staff to understand and use the computer model; a thorough documentation of all underlying assumptions for baseline economics; and a user manual and training material which will facilitate updating of the model in the future.

  11. Direct coal liquefaction baseline design and system analysis

    SciTech Connect

    Not Available

    1990-09-01

    The primary objective of the study is to develop a computer model for a base line direct coal liquefaction design based on two stage direct coupled catalytic reactors. This primary objective is to be accomplished by completing the following: a base line design based on previous DOE/PETC results from Wilsonville pilot plant and other engineering evaluations; a cost estimate and economic analysis; a computer model incorporating the above two steps over a wide range of capacities and selected process alternatives; a comprehensive training program for DOE/PETC Staff to understand and use the computer model; a thorough documentation of all underlying assumptions for baseline economics; and a user manual and training material which will facilitate updating of the model in the future.

  12. Use of ultrasound for enhanced direct coal liquefaction

    SciTech Connect

    Bendale, P.G.; Joseph, S. ); Tierney, J.W.; Wender, I. . Dept. of Chemical and Petroleum Engineering)

    1990-01-01

    The objective of this project is to investigate whether high-intensity ultrasound is capable of inducing coal liquefaction under mild conditions of temperature and pressure, in the presence of a solvent, and in the presence or absence of a liquefaction catalyst. The role of high-intensity ultrasound in effective dispersion of solids and/or activation of catalyst was also investigated. Model compounds which represent coal such as bibenzyl, benzyl ether and anisole in the presence of tetralin or 9,10-dihydroanthracene as a hydrogen donor solvent, were subjected to high-intensity ultrasound to determine if any chemical bonds are broken under the action of ultrasound. Two step liquefaction experiments were carried out to study the effect of ultrasound on both catalyzed and non-catalyzed coal liquefaction (utilizing a bituminous and subbituminous coal). Soluble catalysts such as molybdenum naphthenate or molybdenum carbonyl were used as catalyst precursors along with stoichiometric amounts of elemental sulfur. The results of these experiments with model compounds and with coal are discussed in detail. 25 refs., 6 figs., 16 tabs.

  13. Short contact time direct coal liquefaction using a novel batch reactor. Quarterly report, 1996

    SciTech Connect

    Klein, M.T.; Calkins, W.H.; Huang, H.

    1996-05-01

    The objective of this research is to optimize the design and operation of the bench scale batch reactor (SCTBR) for coal liquefaction at short contact times (0.01 to 10 minutes or longer). Additional objectives are to study the kinetics of direct coal liquefaction particularly at short reaction times, and to investigate the role of the organic oxygen components of coal and their reaction pathways during liquefaction. Many of those objectives have already been achieved and others are still in progress. This quarterly report covers further progress toward those objectives. Much of the previous quarterly report was concerned mainly in the retrograde reactions occurring during the liquefaction process. This report is largely devoted to the kinetics and mechanisms of the liquefaction process itself and the influence of the liquefaction solvents.

  14. Use of dispersed catalysts for direct coal liquefaction

    SciTech Connect

    Hirschon, A.S.; Kim, S.; Wilson, R.B.; Ghaly, O.

    1996-12-31

    With dwindling supplies of petroleum products, efforts to utilize alternative energy feedstocks such as coal, is essential. Several areas in coal conversion technology have been identified that, if improved, could make coal liquefaction more cost competitive with petroleum. The objectives of this project are to address possible improvements in the economics by utilizing low-rank coals, new precursors to dispersed catalysts, and processing variations such as using syngas atmospheres. The purpose of the dispersed catalysts is to better control retrogressive reactions and avoid char formation, while the purpose of the carbon monoxide atmosphere is to improve the economics by simplifying or totally eliminating a separate water-gas-shift step, and perhaps help remove oxygen in the product slate. These possible improvements are being examined and evaluated for potential use in a 2-stage liquefaction process with the goal of converting coal to distillable liquids at a cost competitive to petroleum of $25/bbl. To evaluate our catalysts and process conditions, we used three types of laboratory-scale operations. In the first operation, we compared the reaction chemistry of various ranks of coals and catalysts in synthetic solvents such as hexadecane. This method allowed us to better compare our catalysts without the complications of solvent initiated chemistry. Once the catalysts were tested in this manner, they were examined for the conversions of a Black Thunder subbituminous coal using a recycle vehicle derived from the same coal as the solvent. Finally, we upgraded selected first-stage conversion products using a conventional hydrotreating catalyst to compare with recent results in two-stage coal liquefaction development. The results were evaluated for economic feasibility through a subcontract with Bechtel Corp.

  15. Chemical and toxicologic characterization of co-processing and two-stage direct coal liquefaction materials

    SciTech Connect

    Wright, C.W.; Stewart, D.L.; Mahlum, D.D.; Chess, E.K.; Wilson, B.W.

    1986-03-01

    Recent advances in coal liquefaction have included two-stage direct coal liquefaction processes and petroleum resid/coal co-processing technology. Two-stage coal liquefaction processes are generally comprised of a first-stage thermal or liquefaction reactor followed by a second-stage hydrogenation step. Petroleum resids and coal are simultaneously converted to liquefaction products in co-processing technology. The purpose of this paper is to report the prelimianry results of the chemical analysis and toxicological testing of a coal liquefaction co-processing sample set, and to compare these results to those obtained from two-stage coal liquefaction materials. Samples were chemically characterized by chemical class fractionation, gas chromatography, gas chromatography-mass spectrometry, and low-voltage probe-inlet mass spectrometry. Toxicological activity was measured using the standard histidine reversion microbial mutagenicity test and an initiation/promotion assay for mouse skin tumorigenesis. A brief description of these methods are presented and results are discussed. 9 refs., 2 figs., 3 tabs.

  16. Subtask 3.3 - Feasibility of Direct Coal Liquefaction in the Modern Economic Climate

    SciTech Connect

    Benjamin Oster; Joshua Strege; Marc Kurz; Anthony Snyder; Melanie Jensen

    2009-06-15

    Coal liquefaction provides an alternative to petroleum for the production of liquid hydrocarbon-based fuels. There are two main processes to liquefy coal: direct coal liquefaction (DCL) and indirect coal liquefaction (ICL). Because ICL has been demonstrated to a greater extent than DCL, ICL may be viewed as the lower-risk option when it comes to building a coal liquefaction facility. However, a closer look, based on conversion efficiencies and economics, is necessary to determine the optimal technology. This report summarizes historical DCL efforts in the United States, describes the technical challenges facing DCL, overviews Shenhua's current DCL project in China, provides a DCL conceptual cost estimate based on a literature review, and compares the carbon dioxide emissions from a DCL facility to those from an ICL facility.

  17. Premium distillate products from direct liquefaction of coal

    SciTech Connect

    Zhou, P.Z.; Winschel, R.A.; Klunder, E.B. |

    1994-08-01

    The net liquid products from modern coal liquefaction processes are lower boiling and have much lower end points (mostly under 400{degree}C) than crude petroleum. Coal liquids have very low concentrations of heteroatoms, particularly S, and metals, and are free of resids and asphaltenes. High yields of low-S (0.01--0.03 wt %) naphtha, kerosene, and diesel fuel fractions can be obtained simply by atmospheric distillation, with a total yield of light fuel fractions ranging from 68 to 82 LV% (W260D exclusive). The coal naphtha has a low aromatics content (5--13 LV%), readily meeting projected year-2000 requirements. Its low Reid vapor pressure allows light components from other sources to be blended. The coal light distillate of in appropriate boiling range will be a good low-S blending stock for the light diesel fuel pool. The heavy distillate can be refined into a low-S No. 4 diesel fuel/fuel oil. This fraction, along with the >343{degree}C atmospheric bottoms, can be catalytically cracked or hydrocracked to make light liquid fuels. Thus, modern coal liquids should no longer be envisioned as thick liquids (or even solids) with high concentrations of aromatics and asphaltenes. Products obtained from advanced coal liquefaction technologies are more like light naphthene-base petroleum, but with lower heteroatoms and metals contents, and they are free of resids. Coal liquids are likely to be co-refined in existing petroleum refineries; and hydroprocessing of various severities would be needed for different fractions to produce quality blending stocks for refinery fuel pools.

  18. Preconversion processing of bituminous coals: New directions to improved direct catalytic coal liquefaction. [Effect of pretreatment before liquefaction

    SciTech Connect

    Not Available

    1992-07-01

    The main task of this quarter was to install reactors to conduct preconversion and liquefaction of coal. Coal and coal liquids were collected. The anaerobic chamber (Model 855-AC; Plas Labs, inc.) was procured and set up to store coal samples under an inert gas. Equipment to treat products was assembled, including Soxhlet extraction units, fractionation columns, a distillation column, and a rotary evaporator. Two gas chromatographs for analysis of gases and liquid were adjusted. Two reactor systems were installed for the experimental apparatus. One was Model 4576 high-temperature and high-pressure autoclave (Parr Instrument, 500{degrees}C and 5000 psi) (see Figure 1); the other was a 27 ml of microreactors. The autoclave was obtained from the manufacturer and assembled. The experimental set-up of microreactors are shown in Figure 2.

  19. The role of recycle oil in direct coal liquefaction process development

    SciTech Connect

    Burke, F.P.

    1995-08-01

    It has long been recognized that use of a recycle oil is a convenient and perhaps necessary feature of a practical direct coal liquefaction process. The recycle oil performs a number of important functions. It serves as a vehicle to convey coal into the liquefaction reactor and products from the reactor. It is a medium for mass and heat transfer among the solid, liquid, and gaseous components of the reactor inventory. It can act as a reactant or intermediate in the liquefaction process. Therefore, the nature of the recycle oil can have a determining effect on process configuration and performance, and the characterization of recycle oil composition and chemistry has been the subject of considerable interest. This paper discusses recycle oil characterization and its influence on the industrial development of coal liquefaction technology,

  20. Separation of solids from coal liquefaction products using sonic waves

    SciTech Connect

    Slomka, B.J.

    1994-10-01

    Product streams containing solids are generated in both direct and indirect coal liquefaction processes. This project seeks to improve the effectiveness of coal liquefaction by novel application of sonic and ultrasonic energy to separation of solids from coal liquefaction streams.

  1. Coal liquefaction and hydrogenation

    DOEpatents

    Schindler, Harvey D.; Chen, James M.

    1985-01-01

    Disclosed is a coal liquefaction process using two stages. The first stage liquefies the coal and maximizes the product while the second stage hydrocracks the remainder of the coal liquid to produce solvent.

  2. Preconversion processing of bituminous coals: New directions to improved direct catalytic coal liquefaction

    SciTech Connect

    Not Available

    1993-04-01

    The near equal conversions were obtained even with high coal/liquid ratio (1/3--1/2) for two-step wise high-temperature soaking and the first stage liquefaction. Expected conversions were not observed when vacuum distillation after soaking was used in stead of cyclohexane extraction. This is presumably due to the difficulty with redispersion of vacuum distillated bottoms in the coal liquid, because a batch wise procedure was taken by using glasswares. It is suggested that the proposed procedure in the previous quarter should be tested by a continuous procedure under enough heating conditions to keep low viscosity of the bottoms.

  3. Advanced direct coal liquefaction concepts. Final report, Volume 2

    SciTech Connect

    Berger, D.J.; Parker, R.J.; Simpson, P.L.

    1994-07-01

    Integration of innovative steps into new advanced processes have the potential to reduce costs for producing liquid fuels. In this program, objective is to develop a new approach to liquefaction that generates an all distillate product slate at a reduced cost of about US$25/barrel of crude oil equivalent. A Counterflow Reactor was developed in cooperation with GfK mbH, Germany. Advantages are low hydrogen recycle rates and low feed preheating requirements. Coal/heavy oil slurry is injected into the top of the reactor while the recycle gas and make up hydrogen is introduced into the bottom; hydrogenation products are withdrawn from the top. PU study resulted in distillable oil yields up to 74 wt % on feed (dry ash free) from coprocessing feed slurries containing 40 wt % Vesta subbituminous coal and 60 wt % Cold Lake heavy vacuum tower bottoms. Technologies developed separately by CED and ARC were combined. A 1-kg/hr integrated continuous flow bench scale unit was constructed at the ARC site in Devon, Alberta, based on modifications to a unit at Nisku, Alberta (the modified unit was used in the preliminary economic evaluation).

  4. Conversion of Low-Rank Wyoming Coals into Gasoline by Direct Liquefaction

    SciTech Connect

    Polyakov, Oleg

    2013-12-31

    Under the cooperative agreement program of DOE and funding from Wyoming State’s Clean Coal Task Force, Western Research Institute and Thermosolv LLC studied the direct conversion of Wyoming coals and coal-lignin mixed feeds into liquid fuels in conditions highly relevant to practice. During the Phase I, catalytic direct liquefaction of sub-bituminous Wyoming coals was investigated. The process conditions and catalysts were identified that lead to a significant increase of desirable oil fraction in the products. The Phase II work focused on systematic study of solvothermal depolymerization (STD) and direct liquefaction (DCL) of carbonaceous feedstocks. The effect of the reaction conditions (the nature of solvent, solvent/lignin ratio, temperature, pressure, heating rate, and residence time) on STD was investigated. The effect of a number of various additives (including lignin, model lignin compounds, lignin-derivable chemicals, and inorganic radical initiators), solvents, and catalysts on DCL has been studied. Although a significant progress has been achieved in developing solvothermal depolymerization, the side reactions – formation of considerable amounts of char and gaseous products – as well as other drawbacks do not render aqueous media as the most appropriate choice for commercial implementation of STD for processing coals and lignins. The trends and effects discovered in DCL point at the specific features of liquefaction mechanism that are currently underutilized yet could be exploited to intensify the process. A judicious choice of catalysts, solvents, and additives might enable practical and economically efficient direct conversion of Wyoming coals into liquid fuels.

  5. Coal liquefaction quenching process

    DOEpatents

    Thorogood, Robert M.; Yeh, Chung-Liang; Donath, Ernest E.

    1983-01-01

    There is described an improved coal liquefaction quenching process which prevents the formation of coke with a minimum reduction of thermal efficiency of the coal liquefaction process. In the process, the rapid cooling of the liquid/solid products of the coal liquefaction reaction is performed without the cooling of the associated vapor stream to thereby prevent formation of coke and the occurrence of retrograde reactions. The rapid cooling is achieved by recycling a subcooled portion of the liquid/solid mixture to the lower section of a phase separator that separates the vapor from the liquid/solid products leaving the coal reactor.

  6. Cooperative research program in coal liquefaction

    SciTech Connect

    Huffman, G.P.

    1992-01-01

    Research continues on coal liquefaction in the following areas: (1) Iron Based Catalysts for Coal Liquefaction; (2) Exploratory Research on Coal Conversion; (3) Novel Coal Liquefaction Concepts; (4) Novel Catalysts for Coal Liquefaction. (VC)

  7. Cooperative research program in coal liquefaction

    SciTech Connect

    Huffman, G.P.

    1991-01-01

    This Quarterly Report on coal liquefaction research includes discussion in the areas of (1) Iron Based Catalysts for Coal Liquefaction; (2) Exploratory Research on Coal Conversion; (3) Novel Coal Liquefaction Concepts; (4) Novel Catalysts for Coal Liquefaction. (VC)

  8. Role of iron-based catalyst and hydrogen transfer in direct coal liquefaction

    SciTech Connect

    Xian Li; Shuxun Hu; Lijun Jin; Haoquan Hu

    2008-03-15

    The aim of this research is to understand the major function of iron-based catalysts on direct coal liquefaction (DCL). Pyrolysis and direct liquefaction of Shenhua bituminous coal were carried out to investigate the effect of three solvents (wash-oil from coal-tar, cycle-oil from coal liquefaction, and tetralin) in a N{sub 2} or a H{sub 2} atmosphere and with or without catalyst. The hydrogen content in the solvent and liquid product and the H{sub 2} consumption for every run were calculated to understand the hydrogen transfer approach in DCL. The results showed that the iron-based catalyst promotes the coal pyrolysis, and the dominating function of the catalyst in DCL is to promote the formation of activated hydrogen and to accelerate the secondary distribution of H in the reaction system including the gas, liquid, and solid phases. The major transfer approach of the activated hydrogen is from molecular hydrogen to solvent and then from solvent to coal, and the solvent takes on the role of a 'bridge' in the hydrogen transfer approach. 31 refs., 5 figs., 3 tabs.

  9. Integrated coal liquefaction process

    DOEpatents

    Effron, Edward

    1978-01-01

    In a process for the liquefaction of coal in which coal liquids containing phenols and other oxygenated compounds are produced during the liquefaction step and later hydrogenated, oxygenated compounds are removed from at least part of the coal liquids in the naphtha and gas oil boiling range prior to the hydrogenation step and employed as a feed stream for the manufacture of a synthesis gas or for other purposes.

  10. Investigations into coal coprocessing and coal liquefaction

    SciTech Connect

    Guffey, F.D.; Netzel, D.A.; Miknis, F.P.; Thomas, K.P.; Zhang, Tiejun; Haynes, H.W. Jr.

    1994-06-01

    The conversion of coal to liquid suitable as feedstock to a petroleum refinery is dependent upon several process variables. These variables include temperature, pressure, coal rank, catalyst type, nature of the feed to the reactor, type of process, etc. Western Research Institute (WRI) has initiated a research program in the area of coal liquefaction to address the impact of some of these variables upon the yield and quality of the coal-derived liquid. The principal goal of this research is to improve the efficiency of the coal liquefaction process. Two different approaches are currently being investigated. These include the coprocessing of a heavy liquid, such as crude oil, and coal using a dispersed catalyst and the direct liquefaction of coal using a supported catalyst. Another important consideration in coal liquefaction is the utilization of hydrogen, including both externally- and internally-supplied hydrogen. Because the incorporation of externally-supplied hydrogen during conversion of this very aromatic fossil fuel to, for example, transportation fuels is very expensive, improved utilization of internally-supplied hydrogen can lead to reducing processing costs. The objectives of this investigation, which is Task 3.3.4, Coal Coprocessing, of the 1991--1992 Annual Research Plan, are: (1) to evaluate coal/oil pretreatment conditions that are expected to improve the liquid yield through more efficient dispersion of an oil-soluble, iron-based catalyst, (2) to characterize the coke deposits on novel, supported catalysts after coal liquefaction experiments and to correlate the carbon skeletal structure parameters of the coke deposit with catalyst performance as measured by coal liquefaction product yield, and (3) to determine the modes of hydrogen utilization during coal liquefaction and coprocessing. Experimental results are discussed in this report.

  11. Advanced direct coal liquefaction. Quarterly technical progress report No. 2, December 1983-February 1984

    SciTech Connect

    Paranjape, A.S.

    1984-04-30

    Five Bench-Scale coal liquefaction runs were completed with Wyoming subbituminous coal in a two-stage process scheme. In this process scheme, LDAR, the lighter fraction of ash-free resid, was fed to the catalytic stage prior to its recycle to the thermal stage, whereas DAR, the heavy fraction of the deashed resid, was directly recycled to the thermal stage without any intermediate processing step. The results indicate that increasing coal space rate in the dissolver resulted in lower coal conversion and reduced distillate yield in this process configuration. The coal conversions decreased from 92 wt% to 89 wt% (MAF coal) and the distillate yield was reduced from 50 wt% to less than 40 wt% (MAF coal), as the coal space velocity increased. Attempts to duplicate the yields of Run 32, at comparable process conditions in Runs 37 and 38, were unsuccessful. Several process parameters were investigated but failed to show why the yields of Run 32 could not be duplicated. Valuable process related information was gained as a result of process parameter studies completed during these runs. At comparable process conditions, coal conversions were lower by about 3 to 4 relative percent and were only in the 87 wt% (MAF coal) range. Similarly, the distillate yield was about 40 wt% (MAF coal) which is about 10 wt% lower than observed in Run 32. Although no exact cause for these results could be determined, it appeared that the H/C atomic ratio of the solvent and possibly the flow pattern (plug-flow versus back-mixed) could have affected the coal conversion and quantity of distillate product produced. A significant decrease in coal conversion of 4 to 5 wt% was observed when the disposable catalyst (iron oxide) was removed from the reaction mixture and therefore substantiates the need for a disposable catalyst in the liquefaction of Wyoming subbituminous coal.

  12. Coal Liquefaction Processes.

    ERIC Educational Resources Information Center

    Yen, T. F.

    1979-01-01

    Described is a graduate level engineering course offered at the University of Southern California on coal liquefaction processes. Lecture topics and course requirements are discussed. A 64-item bibliography of papers used in place of a textbook is included. (BT)

  13. Coal liquefaction process

    SciTech Connect

    Minami, R.; Hosoi, T.; Kanou, T.; Okamura, S.; Sunami, Y.

    1984-03-20

    A coal liquefaction process and apparatus therefor are disclosed. According to this invention, a finely divided coal slurry and a solvent are contacted with molecular hydrogen in the presence of a catalyst, the slurry is separated into a gaseous component, a liquid component and a solid residue, the solid residue (which is the liquefaction residue) is then supplied to a molten metal bath together with oxygen gas to generate a gas entraining fine powdery solids, and the thus recovered fine powdery solids are returned to the liquefaction process as a catalyst.

  14. Coal liquefaction process

    DOEpatents

    Carr, Norman L.; Moon, William G.; Prudich, Michael E.

    1983-01-01

    A C.sub.5 -900.degree. F. (C.sub.5 -482.degree. C.) liquid yield greater than 50 weight percent MAF feed coal is obtained in a coal liquefaction process wherein a selected combination of higher hydrogen partial pressure, longer slurry residence time and increased recycle ash content of the feed slurry are controlled within defined ranges.

  15. Method for coal liquefaction

    DOEpatents

    Wiser, Wendell H.; Oblad, Alex G.; Shabtai, Joseph S.

    1994-01-01

    A process is disclosed for coal liquefaction in which minute particles of coal in intimate contact with a hydrogenation catalyst and hydrogen arc reacted for a very short time at a temperature in excess of 400.degree. C. at a pressure of at least 1500 psi to yield over 50% liquids with a liquid to gaseous hydrocarbon ratio in excess of 8:1.

  16. Coal liquefaction and hydrogenation

    DOEpatents

    Schindler, Harvey D.

    1985-01-01

    The coal liquefaction process disclosed uses three stages. The first stage is a liquefaction. The second and third stages are hydrogenation stages at different temperatures and in parallel or in series. One stage is within 650.degree.-795.degree. F. and optimizes solvent production. The other stage is within 800.degree.-840.degree. F. and optimizes the C.sub.5 -850.degree. F. product.

  17. Novel supports for coal liquefaction catalysts

    SciTech Connect

    Haynes, H.W. Jr.

    1992-01-01

    This research is divided into three parts: (1) Evaluation of Alkaline-Earth-Promoted CoMo/Alumina Catalysts in a Bench Scale Hydrotreater, (2) Development of a Novel Catalytic Coal Liquefaction Microreactor (CCLM) Unit, and (3) Evaluation of Novel Catalyst Preparations for Direct Coal Liquefaction. (VC)

  18. Cooperative research in coal liquefaction infratechnology and generic technology development

    SciTech Connect

    Huffman, G.P.; Sendlein, L.V.A.

    1990-01-01

    A summary of research is presented on coal liquefaction. Programs include: bioprocessing of coal, University of Kentucky; materials characterization study of coal liquefaction processes, University of Kentucky; novel approaches to catalysis in coprocessing and in direct liquefaction of coal, University of Pittsburgh; liquefaction research in pyrolysis, catalysis and coal dissolution, West Virginia University; enhanced reactivity and selectivity in coal liquefaction and coprocessing systems, Auburn University; integrated liquefaction/characterization, University of Utah; basic process/resource evaluation task, center for applied energy research; and project integration and database development, University of Kentucky.

  19. Coal liquefaction process

    DOEpatents

    Karr, Jr., Clarence

    1977-04-19

    An improved coal liquefaction process is provided which enables conversion of a coal-oil slurry to a synthetic crude refinable to produce larger yields of gasoline and diesel oil. The process is characterized by a two-step operation applied to the slurry prior to catalytic desulfurization and hydrogenation in which the slurry undergoes partial hydrogenation to crack and hydrogenate asphaltenes and the partially hydrogenated slurry is filtered to remove minerals prior to subsequent catalytic hydrogenation.

  20. Coal Liquefaction desulfurization process

    DOEpatents

    Givens, Edwin N.

    1983-01-01

    In a solvent refined coal liquefaction process, more effective desulfurization of the high boiling point components is effected by first stripping the solvent-coal reacted slurry of lower boiling point components, particularly including hydrogen sulfide and low molecular weight sulfur compounds, and then reacting the slurry with a solid sulfur getter material, such as iron. The sulfur getter compound, with reacted sulfur included, is then removed with other solids in the slurry.

  1. Method for coal liquefaction

    DOEpatents

    Wiser, W.H.; Oblad, A.G.; Shabtai, J.S.

    1994-05-03

    A process is disclosed for coal liquefaction in which minute particles of coal in intimate contact with a hydrogenation catalyst and hydrogen arc reacted for a very short time at a temperature in excess of 400 C at a pressure of at least 1500 psi to yield over 50% liquids with a liquid to gaseous hydrocarbon ratio in excess of 8:1. 1 figures.

  2. The kinetics of catalytic hydrogenation of pyrene-implications for direct coal liquefaction processing

    SciTech Connect

    Stephens, H.P.; Chapman, R.N.

    1983-01-01

    Although recycling heavy solvents has recently re-emerged as a key to cutting the cost of direct coal liquefaction, little data for the hydrogenation of heavy solvent donors have been reported. This study addresses the kinetic and thermodynamic aspects of catalytic hydrogenation of pyrene, a donor solvent precursor thought to play an important role in coal liquefaction processes that use heavy recycle solvents. In the presence of a catalyst, pyrene (Py) is hydrogenated to di- (H/sub 2/Py), tetra- (H/sub 4/Py), hexa- (H/sub 6/Py), deca- (H/sub 10/Py) and perhydro- (H/sub 16/Py) species via a complex mechanism involving a network of reversible parallel and series reactions. Though several studies have dealt with aspects of pyrene hydrogenation, including hydrocracking reactions, reaction product distributions and thermodynamic properties, the kinetics of hydrogenation have not been previously reported. Ultimate application of kinetic and thermodynamic data to direct coal liquefaction must take into consideration the conditions imposed by the particular process used. However, two generalizations may be made regarding hydrogen supplied by the dihydropyrene component of donor solvents: (1) Increasing hydrogen partial pressure increases both the rate at which H/sub 2/Py is formed and the equilibrium concentration of H/sub 2/Py. Therefore, pyrene rehydrogenation should be done at as high a pressure as is cost effective. Although an increase in temperature favors the rate of attainment of equilibrium between Py and H/sub 2/Py, the position of the equilibrium is shifted toward pyrene. Temperature must therefore be adjusted to achieve an optimum trade-off between rate of formation and maximum possible concentration of H/sub 2/Py.

  3. Studies of the initial reactions that occur during direct coal liquefaction

    SciTech Connect

    Stohl, F.V.

    1989-01-01

    Reactions that occur during preconversion processing of coal in direct liquefaction can be either beneficial or harmful. The objectives of this work are to identify the types of compounds and process conditions that give rise to retrogressive reactions during preconversion processing. Experiments have been performed to evaluate the impacts of temperature, catalysts, mineral matter, and hydrogen donors on these reactions. Initial studies have been carried out using dibenzyl ether (DBE) because ether linkages represent one type of bonding believed to be present in coal (1). Previous studies have analyzed the kinetics and mechanisms of thermolysis of DBE (2,3) and have also used DBE to study effects of process variables in coal liquefaction (4). Results of thermal reactions with DBE have shown that the main reaction products are toluene, benzaldehyde, benzyl alcohol and benzene (2). In the presence of catalysts such as ZnCl/sub 2/, the product distributions are more complicated and can obtain significant amounts of material with higher molecular weights than DBE (5,6). 8 refs., 2 tabs.

  4. Coal liquefaction with coal tar solvent

    SciTech Connect

    Gir, S.; Rhodes, D.E.

    1986-12-16

    A method is described of liquefying coal, comprising: mixing solid coal with a process solvent comprising coal tar material which has been at least partially hydrogenated under conditions which selectively hydrogenate aromatic coal tar components to hydroaromatics and which preserve the integrity of organonitrogen coal tar components, to produce a coal-solvent slurry; treating the coal-solvent slurry under coal-liquefying conditions in a liquefaction zone to produce a solution containing coal liquefaction products; and recovering coal liquefaction products from the solution.

  5. Use of ultrasound for enhanced direct coal liquefaction: Quarterly report, August 1988--December 1988

    SciTech Connect

    Not Available

    1989-01-01

    The objective of this project is to investigate whether high-intensity ultrasound is capable of inducing coal liquefaction under mild conditions of temperature and pressure in the presence of a solvent and in the presence or absence of a liquefaction catalyst. The role of high-intensity ultrasound in effective dispersion of solids and/or activation of catalysts will also be investigated using an appropriate liquefaction catalyst. The study will be conducted in two parts. First model compounds (bibenzyl and benzyl phenyl ether) will be subjected to high-intensity ultrasound to determine if any chemical bonds are broken under the action of ultrasound. In the second part, the effect of ultrasound on both catalyzed and non-catalyzed coal liquefaction will be determined. Two coals (sub-bituminous and bituminous) will be studied using tetralin as a hydrogen donating solvent and molybdenum sulfide as catalyst. 3 refs., 3 figs.

  6. Coal liquefaction process

    DOEpatents

    Wright, C.H.

    1986-02-11

    A process is described for the liquefaction of coal wherein raw feed coal is dissolved in recycle solvent with a slurry containing recycle coal minerals in the presence of added hydrogen at elevated temperature and pressure. The highest boiling distillable dissolved liquid fraction is obtained from a vacuum distillation zone and is entirely recycled to extinction. Lower boiling distillable dissolved liquid is removed in vapor phase from the dissolver zone and passed without purification and essentially without reduction in pressure to a catalytic hydrogenation zone where it is converted to an essentially colorless liquid product boiling in the transportation fuel range. 1 fig.

  7. Coal liquefaction process

    DOEpatents

    Wright, Charles H.

    1986-01-01

    A process for the liquefaction of coal wherein raw feed coal is dissolved in recycle solvent with a slurry containing recycle coal minerals in the presence of added hydrogen at elevated temperature and pressure. The highest boiling distillable dissolved liquid fraction is obtained from a vacuum distillation zone and is entirely recycled to extinction. Lower boiling distillable dissolved liquid is removed in vapor phase from the dissolver zone and passed without purification and essentially without reduction in pressure to a catalytic hydrogenation zone where it is converted to an essentially colorless liquid product boiling in the transportation fuel range.

  8. Coal liquefaction process

    DOEpatents

    Maa, Peter S.

    1978-01-01

    A process for liquefying a particulate coal feed to produce useful petroleum-like liquid products which comprises contacting; in a series of two or more coal liquefaction zones, or stages, graded with respect to temperature, an admixture of a polar compound; or compounds, a hydrogen donor solvent and particulate coal, the total effluent being passed in each instance from a low temperature zone, or stage to the next succeeding higher temperature zone, or stage, of the series. The temperature within the initial zone, or stage, of the series is maintained about 70.degree. F and 750.degree. F and the temperature within the final zone, or stage, is maintained between about 750.degree. F and 950.degree. F. The residence time within the first zone, or stage, ranges, generally, from about 20 to about 150 minutes and residence time within each of the remaining zones, or stages, of the series ranges, generally, from about 10 minutes to about 70 minutes. Further steps of the process include: separating the product from the liquefaction zone into fractions inclusive of a liquid solvent fraction; hydrotreating said liquid solvent fraction in a hydrogenation zone; and recycling the hydrogenated liquid solvent mixture to said coal liquefaction zones.

  9. Coal liquefaction process streams characterization and evaluation

    SciTech Connect

    Robbins, G.A.; Brandes, S.D.; Winschel, R.A.; Burke, F.P.

    1991-11-01

    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.

  10. Coal liquefaction process streams characterization and evaluation

    SciTech Connect

    Brandes, S.D.; Winschel, R.A.; Burke, F.P.; Robbins, G.A.

    1991-09-01

    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.

  11. Coal liquefaction process streams characterization and evaluation

    SciTech Connect

    Robbins, G.A.; Brandes, S.D.; Winschel, R.A.; Burke, F.P.

    1992-03-01

    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.

  12. Preconversion processing of bituminous coals: New directions to improved direct catalytic coal liquefaction. [Effect of preconversion heat soak with coal liquids

    SciTech Connect

    Not Available

    1992-07-01

    A study of the high-temperature soaking started in this quarter, following the installation of reactors in the previous quarter. Two high-volatile bituminous coals and three coal liquids, which were identified in the previous report, were used. A cross-linked, three-dimensional macromolecular model has been widely accepted f or the structure of coal, but there is no direct evidence to prove this model. The conventional coal structure model has been recently re-examined by this investigator because of the importance of relatively strong intra- and intermolecular interactions in bituminous coals. It was reasonable to deduce that significant portions were physically associated after a study of multistep extractions, associative equilibria, the irreversibility and the dependence of coal concentration on solvent swelling, and consideration of the monophase concept. Physical dissociation which may be significant above 300{degree}C should be utilized for the treatment before liquefaction. The high-temperature soaking in a recycle oil was proposed to dissociate coal complexes.

  13. Direct coal liquefaction baseline design and system analysis. Quarterly report, April--June 1991

    SciTech Connect

    Not Available

    1991-07-01

    The primary objective of the study is to develop a computer model for a base line direct coal liquefaction design based on two stage direct coupled catalytic reactors. This primary objective is to be accomplished by completing the following: a base line design based on previous DOE/PETC results from Wilsonville pilot plant and other engineering evaluations; a cost estimate and economic analysis; a computer model incorporating the above two steps over a wide range of capacities and selected process alternatives; a comprehensive training program for DOE/PETC Staff to understand and use the computer model; a thorough documentation of all underlying assumptions for baseline economics; and a user manual and training material which will facilitate updating of the model in the future.

  14. Direct coal liquefaction baseline design and system analysis. Quarterly report, September--December 1990

    SciTech Connect

    Not Available

    1991-01-01

    The primary objective of the study is to develop a computer model for a base line direct coal liquefaction design based on two stage direct coupled catalytic reactors. This primary objective is to be accomplished by completing the following: a base line design based on previous DOE/PETC results from Wilsonville pilot plant and other engineering evaluations; a cost estimate and economic analysis; a computer model incorporating the above two steps over a wide range of capacities and selected process alternatives; a comprehensive training program for DOE/PETC Staff to understand and use the computer model; a thorough documentation of all underlying assumptions for baseline economics; and a user manual and training material which will facilitate updating of the model in the future.

  15. Production and Optimization of Direct Coal Liquefaction derived Low Carbon-Footprint Transportation Fuels

    SciTech Connect

    Steven Markovich

    2010-06-30

    This report summarizes works conducted under DOE Contract No. DE-FC26-05NT42448. The work scope was divided into two categories - (a) experimental program to pretreat and refine a coal derived syncrude sample to meet transportation fuels requirements; (b) system analysis of a commercial scale direct coal liquefaction facility. The coal syncrude was derived from a bituminous coal by Headwaters CTL, while the refining study was carried out under a subcontract to Axens North America. The system analysis included H{sub 2} production cost via six different options, conceptual process design, utilities requirements, CO{sub 2} emission and overall plant economy. As part of the system analysis, impact of various H{sub 2} production options was evaluated. For consistence the comparison was carried out using the DOE H2A model. However, assumptions in the model were updated using Headwaters database. Results of Tier 2 jet fuel specifications evaluation by the Fuels & Energy Branch, US Air Force Research Laboratory (AFRL/RZPF) located at Wright Patterson Air Force Base (Ohio) are also discussed in this report.

  16. Fuel-blending stocks from the hydrotreatment of a distillate formed by direct coal liquefaction

    SciTech Connect

    Andile B. Mzinyati

    2007-09-15

    The direct liquefaction of coal in the iron-catalyzed Suplex process was evaluated as a technology complementary to Fischer-Tropsch synthesis. A distinguishing feature of the Suplex process, from other direct liquefaction processes, is the use of a combination of light- and heavy-oil fractions as the slurrying solvent. This results in a product slate with a small residue fraction, a distillate/naphtha mass ratio of 6, and a 65.8 mass % yield of liquid fuel product on a dry, ash-free coal basis. The densities of the resulting naphtha (C{sub 5}-200{sup o}C) and distillate (200-400{sup o}C) fractions from the hydroprocessing of the straight-run Suplex distillate fraction were high (0.86 and 1.04 kg/L, respectively). The aromaticity of the distillate fraction was found to be typical of coal liquefaction liquids, at 60-65%, with a Ramsbottom carbon residue content of 0.38 mass %. Hydrotreatment of the distillate fraction under severe conditions (200{sup o}C, 20.3 MPa, and 0.41 g{sub feed} h{sup -1} g{sub catalyst}{sup -1}) with a NiMo/Al{sub 2}O{sub 3} catalyst gave a product with a phenol content of {lt}1 ppm, a nitrogen content {lt}200 ppm, and a sulfur content {lt}25 ppm. The temperature was found to be the main factor affecting diesel fraction selectivity when operating at conditions of WHSV = 0.41 g{sub feed} h{sup -1} g{sub catalyst}{sup -1} and PH{sub 2} = 20.3 MPa, with excessively high temperatures (T {gt} 420{sup o}C) leading to a decrease in diesel selectivity. The fuels produced by the hydroprocessing of the straight-run Suplex distillate fraction have properties that make them desirable as blending components, with the diesel fraction having a cetane number of 48 and a density of 0.90 kg/L. The gasoline fraction was found to have a research octane number (RON) of 66 and (N + 2A) value of 100, making it ideal as a feedstock for catalytic reforming and further blending with Fischer-Tropsch liquids. 44 refs., 9 figs., 12 tabs.

  17. Viscosity Depressants for Coal Liquefaction

    NASA Technical Reports Server (NTRS)

    Kalfayan, S. H.

    1983-01-01

    Proposed process modification incorporates viscosity depressants to prevent coal from solidifying during liquefaction. Depressants reduce amount of heat needed to liquefy coal. Possible depressants are metallic soaps, such as stearate, and amides, such as stearamide and dimer acid amides.

  18. Effect of solvent characteristics on coal liquefaction

    SciTech Connect

    Huang, He; Wang, Shaojie; Wang, Keyu; Klein, M.T.; Calkins, W.H.

    1996-12-31

    It has been known for a long time that the characteristics of the liquefaction solvent has a profound effect on direct coal liquefaction. The amount of hydrogen consumed during the liquefaction process, the degree and quantity of retrograde reactions that occur, and the quality of the liquid products are all influenced by the process solvent. A number of analytical approaches have been developed to determine the important characteristics of the solvent for coal liquefaction. The hydrogen donor ability has clearly been important. However, such other characteristics of a liquefaction solvent as solubility parameter, content and type of higher aromatic hydrocarbons, and phenolic content have also been found to be significant. Finseth et al. have shown that the bulk of the hydrogen consumed from an uncatalyzed donor solvent liquefaction above 400{degrees}C is consumed in gas generation, heteroatom removal and hydrogenolysis of the coal matrix. Wilson et al. have also shown that the major role of hydrogen in uncatalyzed liquefaction is consumed by alkyl fission and hydrogenolysis reactions and not with hydrogenating aromatic rings. McMillan et al. have postulated that a radical hydrogen transfer process along with donor solvent capping of thermally produced radicals from the coal as possible processes involved with the hydroaromatic donor solvents in coal liquefaction. With the development of a short contact time batch reactor (SCTBR), determining the influence of the processing solvent on the liquefaction rates, conversion profiles and the quality of the liquid product at a particular time became possible. The influence of type of solvent, combined with other effects, such as gas atmosphere (i.e., in hydrogen and in nitrogen) and catalyst, on the coal liquefaction is reported in this paper.

  19. Coal liquefaction and gas conversion: Proceedings. Volume 1

    SciTech Connect

    Not Available

    1993-12-31

    Volume I contains papers presented at the following sessions: AR-Coal Liquefaction; Gas to Liquids; and Direct Liquefaction. Selected papers have been processed separately for inclusion in the Energy Science and Technology Database.

  20. Cooperative research in coal liquefaction

    SciTech Connect

    Huffman, G.P.; Sendlein, L.V.A.

    1991-05-28

    Significant progress was made in the May 1990--May 1991 contract period in three primary coal liquefaction research areas: catalysis, structure-reactivity studies, and novel liquefaction processes. A brief summary of the accomplishments in the past year in each of these areas is given.

  1. Short contact time direct coal liquefaction using a novel batch reactor. Quarterly technical progress report, September 15, 1995--January 15, 1996

    SciTech Connect

    Klein, M.T.; Calkins, W.H.; Huang, He

    1996-01-26

    The objective of this research is to optimize the design and operation of the bench scale batch reactor (SCTBR) f or coal liquefaction at short contact times (0.01 to 10 minutes or longer). Additional objectives are to study the kinetics of direct coal liquefaction particularly at short reaction times, and to investigate the role of the organic oxygen components of coal and their reaction pathways during liquefaction. Many of those objectives have already been achieved and others are still in progress. This quarterly report covers further progress toward those objectives.

  2. Two stage liquefaction of coal

    DOEpatents

    Neuworth, Martin B.

    1981-01-01

    A two stage coal liquefaction process and apparatus comprising hydrogen donor solvent extracting, solvent deashing, and catalytic hydrocracking. Preferrably, the catalytic hydrocracking is performed in an ebullating bed hydrocracker.

  3. Steam pretreatment for coal liquefaction

    NASA Astrophysics Data System (ADS)

    Ivanenko, Olga

    The objectives of this work are to test the application of steam pretreatment to direct coal liquefaction, to investigate the reaction of model compounds with water, and to explore the use of zeolites in these processes. Previous work demonstrated the effectiveness of steam pretreatment in a subsequent flash pyrolysis. Apparently, subcritical steam ruptures nearly all of the ether cross links, leaving a partially depolymerized structure. It was postulated that very rapid heating of the pretreated coal to liquefaction conditions would be required to preserve the effects of such treatment. Accordingly, a method was adopted in which coal slurry is injected into a hot autoclave containing solvent. Since oxygen is capable of destroying the pretreatment effect, precautions were taken for its rigorous exclusion. Tests were conducted with Illinois No. 6 coal steam treated at 340sp°C, 750 psia for 15 minutes. Both raw and pretreated samples were liquified in deoxygenated tetralin at high severity (400sp°C, 30 min.) and low severity (a: 350sp°C, 30 min., and b: 385sp°C, 15 min.) conditions under 1500 psia hydrogen. Substantial improvement in liquid product quality was obtained and the need for rapid heating and oxygen exclusion demonstrated. Under low severity conditions, the oil yield was more than doubled, going from 12.5 to 29 wt%. Also chemistry of the pretreatment process was studied using aromatic ethers as model compounds. alpha-Benzylnaphthyl ether (alpha-BNE), alpha-naphthylmethyl phenyl (alpha-NMPE), and 9-phenoxyphenanthrene were exposed to steam and inert gas at pretreatment conditions and in some cases to liquid water at 315sp°C. alpha-BNE and alpha-NMPE showed little difference in conversion in inert gas and in steam. Hence, these compounds are poor models for coal in steam pretreatment. Thermally stable 9-phenoxyphenanthrene, however, was completely converted in one hour by liquid water at 315sp°C. At pretreatment conditions mostly rearranged starting

  4. DIRECT LIQUEFACTION PROOF-OF-CONCEPT PROGRAM

    SciTech Connect

    A.G. Comolli; T.L.K. Lee; J. Hu; G. Popper; M.D. Elwell; J. Miller; D. Parfitt; P. Zhou

    1999-12-30

    This report presents the results of the bench-scale work, Bench Run PB-09, HTI Run Number 227-106, conducted under the DOE Proof-of-Concept Option Program indirect coal liquefaction at Hydrocarbon Technologies Inc. in Lawrenceville, New Jersey. Bench Run PB-09 was conducted using two types of Chinese coal, Shenhua No.2 and Shenhua No.3, and had several goals. One goal was to study the liquefaction performance of Shenhua No.2 and Shenhua No.3 with respect to coal conversion and distillate production. Another goal of Bench Run PB-09 was to study the effect of different GelCatw formulations and loadings. At the same time, the space velocity and the temperature of the fmt reactor, K-1, were varied to optimize the liquefaction of the two Chinese coals. The promoter-modified HTI GelCat{trademark} catalyst was very effective in the direct liquefaction of coal with nearly 92% maf coal conversion with Shenhua No.3 and 93% maf coal conversion with 9 Shenhua No.2. Distillate yields (CQ-524 C)varied from 52-68% maf for Shenhua No.3 coal to 54-63% maf for Shenhua No.2 coal. The primary conclusion from Bench Run PB-09 is that Shenhua No.3 coal is superior to Shenhua No.2 coal in direct liquefaction due to its greater distillate production, although coal conversion is slightly lower and C{sub 1}-C{sub 3} light gas production is higher for Shenhua No.3. The new promoter modified GelCat{trademark} proved successful in converting the two 9 Chinese coals and, under some conditions, producing good distillate yields for a coal-only bench run. Run PB-09 demonstrated significantly better performance of China Shenhua coal using HTI's coal direct liquefaction technology and GelCat{trademark} catalyst than that obtained at China Coal Research Institute (CCRI, coal conversion 88% and distillate yield 61%).

  5. Coal liquefaction and gas conversion contractors review conference: Proceedings

    SciTech Connect

    1995-11-01

    This volume contains 55 papers presented at the conference. They are divided into the following topical sections: Direct liquefaction; Indirect liquefaction; Gas conversion (methane conversion); and Advanced research liquefaction. Papers in this last section deal mostly with coprocessing of coal with petroleum, plastics, and waste tires, and catalyst studies. Selected papers are indexed separately for inclusion in the Energy Science and Technology Database.

  6. Preconversion processing of bituminous coals: New directions to improved direct catalytic coal liquefaction. Quarterly report, January 1, 1992--March 31, 1992

    SciTech Connect

    Not Available

    1992-07-01

    A study of the high-temperature soaking started in this quarter, following the installation of reactors in the previous quarter. Two high-volatile bituminous coals and three coal liquids, which were identified in the previous report, were used. A cross-linked, three-dimensional macromolecular model has been widely accepted f or the structure of coal, but there is no direct evidence to prove this model. The conventional coal structure model has been recently re-examined by this investigator because of the importance of relatively strong intra- and intermolecular interactions in bituminous coals. It was reasonable to deduce that significant portions were physically associated after a study of multistep extractions, associative equilibria, the irreversibility and the dependence of coal concentration on solvent swelling, and consideration of the monophase concept. Physical dissociation which may be significant above 300{degree}C should be utilized for the treatment before liquefaction. The high-temperature soaking in a recycle oil was proposed to dissociate coal complexes.

  7. Short contact time direct coal liquefaction using a novel batch reactor. Progress report, May 16, 1994--September 15, 1994

    SciTech Connect

    Klein, M.T.; Calkins, W.H.

    1994-09-30

    The objective of this research is to optimize the design and operation of the bench scale batch reactor (SCTBR) for coal liquefaction at short contact times (0.01 to 10 minutes or longer). This reactor is simple enough and low enough in cost to serve as a suitable replacement for the traditional tubing-bomb reactors for many coal liquefaction and other high-pressure, high-temperature reaction studies. The liquefaction of selected Argonne Premium coals and the role of organic oxygen components of the coal and their reaction pathways at very low conversions are being investigated.

  8. Advanced direct coal liquefaction concepts. Quarterly report, April 1, 1993--June 30, 1993

    SciTech Connect

    Berger, D.J.; Parker, R.J.; Simpson, P.L. |

    1993-11-01

    Construction and commissioning of the bench unit for operation of the first stage of the process was completed. Solubilization of Black Thunder coal using carbon monoxide and steam was successfully demonstrated in the counterflow reactor system. The results were comparable with those obtained in the autoclave with the exception that coal solubilization at the same nominal residence times was slightly lower. The bench unit has now been modified for two stage operation. The Wilsonville process derived solvent for Black Thunder coal (V-1074) was found to be essentially as stable as the previous solvent used in the autoclave runs (V-178 + 320) at reactor conditions. This solvent (V-1074) is, therefore, being used in the bench unit tests. Carbon monoxide may be replaced by synthesis gas for the coal solubilization step in the process. However, in autoclave tests, coal conversion was found to be dependent on the amount of carbon monoxide present in the synthesis gas. Coal conversions ranged from 88% for pure carbon monoxide to 67% for a 25:75 carbon monoxide/hydrogen mixture at equivalent conditions. Two stage liquefaction tests were completed in the autoclave using a disposable catalyst (FeS) and hydrogen in the second stage. Increased coal conversion, higher gas and oil and lower asphaltene and preasphaltene yields were observed as expected. However, no hydrogen consumption was observed in the second stage. Other conditions, in particular, alternate catalyst systems will be explored.

  9. Fine particle clay catalysts for coal liquefaction

    SciTech Connect

    Olson, E.S.

    1991-01-01

    The efficient production of environmentally acceptable distillate fuels requires catalysts for hydrogenation and cleavage of the coal macromolecules and removal of oxygen, nitrogen, and sulfur heteroatoms. The goal of the proposed research is to develop new catalysts for the direct liquefaction of coal. This type of catalyst consists of fine clay particles that have been treated with reagents which form pillaring structures between the aluminosilicate layers of the clay. The pillars not only hold the layers apart but also constitute the active catalytic sites for hydrogenation of the coal and the solvent used in the liquefaction. The pillaring catalytic sites are composed of pyrrhotite, which has been previously demonstrated to be active for coal liquefaction. The pyrrhotite sites are generated in situ by sulfiding the corresponding oxyiron species. The size of the catalyst will be less than 40 nm in order to promote intimate contact with the coal material. Since the clays and reagents for pillaring and activating the clays are inexpensive, the catalysts can be discarded after use, rather than regenerated by a costly process. The proposed work will evaluate methods for preparing the fine particle iron-pillared clay dispersions and for activating the particles to generate the catalysts. Characterization studies of the pillared clays and activated catalysts will be performed. The effectiveness of the pillared clay dispersion for hydrogenation and coal liquefaction will be determined in several types of testing.

  10. Fine particle clay catalysts for coal liquefaction

    SciTech Connect

    Olson, E.S.

    1991-01-01

    The efficient production of environmentally acceptable distillate fuels requires catalysts for hydrogenation and cleavage of the coal macromolecules and removal of oxygen, nitrogen, and sulfur heteroatoms. The goal of the proposed research is to develop new catalysts for the direct liquefaction of coal. This type of catalyst consists of fine clay particles that have been treated with reagents which form pillaring structures between the aluminosilicate layers of the clay. The pillars not only hold the layers apart but also constitute the active catalytic sites for hydrogenation of the coal and solvent used in the liquefaction. The pillaring catalytic sites are composed of pyrrhotite, which has been previously demonstrated to be active for coal liquefaction. The pyrrhotite sites are generated in situ by sulfiding the corresponding oxyiron species. The size of the catalyst will be less than 40 nm in order to promote intimate contact with the coal material. Since the clays and reagents for pillaring and activating the clays are inexpensive, the catalysts can be discarded after use, rather than regenerated by a costly process. The proposed work will evaluate methods for preparing the fine particle iron-pillared clay dispersions and for activating the particles to generate the catalysts. Characterization studies of the pillared clays and activated catalysts will performed. The effectiveness of the pillared clay dispersion for hydrogenation and coal liquefaction will be determined in several types of testing. 5 refs., 1 tab.

  11. Studies of the initial reactions that occur during direct coal liquefaction

    SciTech Connect

    Stohl, F.V.

    1989-01-01

    The objectives of this work are to identify the types of compounds and process conditions that give rise to retrogressive reactions during preconversion processing. Experiments have been performed to evaluate the impacts of temperature, pressure, catalysts, mineral matter, and hydrogen donor on these reactions. Initial studies have been carried out using dibenzyl ether (DBE) because ether linkages represent one type of bonding believed to be present in coal. Previous studies have analyzed the kinetics and mechanism of thermolysis of DBE and have also used DBE to study effects of process variables in coal liquefaction. Results of thermal reactions with DBE have shown that the main reaction products are toluene, benzaldehyde, benzyl alcohol and benzene. In the presence of catalysts such as ZnCl{sub 2}, the product distributions are more complicated and can contain significant amounts of material with higher molecular weights than DBE. 8 refs., 8 figs.

  12. Liquefaction of sub-bituminous coal

    DOEpatents

    Schindler, Harvey D.; Chen, James M.

    1986-01-01

    Sub-bituminous coal is directly liquefied in two stages by use of a liquefaction solvent containing insoluble material as well as 850.degree. F.+ material and 850.degree. F.- material derived from the second stage, and controlled temperature and conversion in the second stage. The process is in hydrogen balance.

  13. Surfactant-Assisted Coal Liquefaction

    NASA Technical Reports Server (NTRS)

    Hickey, Gregory S.; Sharma, Pramod K.

    1993-01-01

    Obtaining liquid fuels from coal which are economically competitive with those obtained from petroleum based sources is a significant challenge for the researcher as well as the chemical industry. Presently, the economics of coal liquefaction are not favorable because of relatively intense processing conditions (temperatures of 430 degrees C and pressures of 2200 psig), use of a costly catalyst, and a low quality product slate of relatively high boiling fractions. The economics could be made more favorable by achieving adequate coal conversions at less intense processing conditions and improving the product slate. A study has been carried out to examine the effect of a surfactant in reducing particle agglomeration and improving hydrodynamics in the coal liquefaction reactor to increase coal conversions...

  14. Preconversion processing of bituminous coals: New directions to improved direct catalytic coal liquefaction. Final report, September 20, 1991--September 19, 1993

    SciTech Connect

    Not Available

    1993-09-01

    One of the main goals for competitive coal liquefaction is to decrease gas yields to reduce hydrogen consumption. Complexing this element as methane and ethane decreases process efficiently and is less cost effective. To decrease the gas yield and increase the liquid yield, an effective preconversion process has been explored on the basis of the physically associated molecular nature of coal. Activities have been focused on two issues: (1) maximizing the dissolution of associated coal and (2) defining the different reactivity associated with a wide molecular weight distribution. Two-step soaking at 350{degrees}C and 400{degrees}C in a recycle oil was found to be very effective for coal solubilization. No additional chemicals, catalysts, and hydrogen are required for this preconversion process. High-volatile bituminous coals tested before liquefaction showed 80--90% conversion with 50--55% oil yields. New preconversion steps suggested are as follows: (1) dissolution of coal with two-step high-temperature soaking, (2) separation into oil and heavy fractions of dissolved coal with vacuum distillation, and (3) selective liquefaction of the separated heavy fractions under relatively mild conditions. Laboratory scale tests of the proposed procedure mode using a small autoclave showed a 30% increase in the oil yield with a 15--20% decrease in the gas yield. This batch operation projects a substantial reduction in the ultimate cost of coal liquefaction.

  15. Surfactant-assisted coal liquefaction

    NASA Technical Reports Server (NTRS)

    Hsu, G. C.

    1977-01-01

    Improved process of coal liquefaction utilizing nonaqueous surfactant has increased oil yield from 50 to about 80%. Asphaltene molecule formation of colloid particles is prevented by surfactant. Separated molecules present more surface area for hydrogenation reaction. Lower requirements for temperature, pressure, and hydrogen lead to reduction in capital and operation costs.

  16. ENVIRONMENTAL ASSESSMENT OF COAL LIQUEFACTION

    EPA Science Inventory

    The report summarizes results of a study of the environmental aspects of 14 of the most prominent coal liquefaction systems, in terms of background, process description, major operations, input and output streams, status, and schedule of system development. As a result of the stu...

  17. Coal liquefaction process streams characterization and evaluation

    SciTech Connect

    Robbins, G.A.; Winshel, R.A.; Burke, F.P.

    1990-10-01

    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 first objective will utilize analytical techniques which have not been fully demonstrated; the second objective involves more previously proven methods. This quarter, two feed coals and 39 process oils from Wilsonville Run 258 were analyzed to provide information on process performance. Run 258 was operated in the thermal/catalytic Close-Coupled Integrated Two-Stage Liquefaction (CC-ITSL) mode with ash recycle. The subbituminous feed coals were from the Spring Creek Mine (Anderson and Dietz seams) and from the Black Thunder Mine (Wyodak and Anderson seams). Shell 324 catalyst was used in the second stage. Various coal samples related to Wilsonville Run 259 were analyzed for chemical and petrographic composition. These results will be given in a future report, which covers all of Run 259. 18 figs., 24 tabs.

  18. A Characterization and Evaluation of Coal Liquefaction Process Streams

    SciTech Connect

    G. A. Robbins; R. A. Winschel; S. D. Brandes

    1998-06-09

    CONSOL characterized 38 process strea m samples from HTI Run PB- 04, in which Black Thunder Mine Coal, Hondo vacuum resid, autom obile shredder residue (ASR), and virgin plastics were used as liquefaction feedstocks with dispersed catalyst. A paper on kinetic modeling of resid reactivity was presented at the DOE Coal Lique -faction and Solid Fuels Contractors Review Conference, September 3- 4, 1997, i n Pittsburgh, PA. The paper, "The Reactivity of Direct Coal Liquefaction Resids", i s appended (Appendix 1). Three papers on characterization of samples from coal/ resid/ waste p lastics co- liquefaction were presented or submitted for presen tation at conferences. Because of their similarity, only one of the papers is appended to this report. The paper, "Characterization o f Process Samples From Co- Liquefaction of Coal and Waste Polymers", (Appendix 2) was presented at the DOE Coal Liquefaction and Solid Fuels C ontractors Review Conference, September 3- 4, 1997, in Pittsburgh, PA. The paper, "Characterization of Process Stream Samples From Bench- Scale Co -Liquefaction Runs That Utilized Waste Polymers as Feedstocks" was presented at the 214th National Meeting of the Ameri can Chemical Society, September 7- 11, 1997, in Las Vegas, NV. The paper, "Characterization of Process Oils from Coal/ Waste Co- Liquefaction" wa s submitted for presentation at the 14th Japan/ U. S. Joint Technical Meeting on Coa l Liquefaction and Materials for Coal Liquefaction on October 28, 1997, in Tokyo, Japan. A joint Burns and Roe Services Corp. and CONSOL pap er on crude oil assays of product oils from HTI Run PB- 03 was presented at the DOE Coal Liquefaction and Solid Fuel s Contractors Review Conference, September 3- 4, 1997, in Pittsburgh, PA. The paper , "Characterization of Liquid Products from All- Slurry Mode Liquefaction", is appende d (Appendix 3).

  19. Iron catalyzed coal liquefaction process

    DOEpatents

    Garg, Diwakar; Givens, Edwin N.

    1983-01-01

    A process is described for the solvent refining of coal into a gas product, a liquid product and a normally solid dissolved product. Particulate coal and a unique co-catalyst system are suspended in a coal solvent and processed in a coal liquefaction reactor, preferably an ebullated bed reactor. The co-catalyst system comprises a combination of a stoichiometric excess of iron oxide and pyrite which reduce predominantly to active iron sulfide catalysts in the reaction zone. This catalyst system results in increased catalytic activity with attendant improved coal conversion and enhanced oil product distribution as well as reduced sulfide effluent. Iron oxide is used in a stoichiometric excess of that required to react with sulfur indigenous to the feed coal and that produced during reduction of the pyrite catalyst to iron sulfide.

  20. Coal liquefaction process streams characterization and evaluation

    SciTech Connect

    Campbell, J.A.; Linehan, J.C.; Robins, W.H. )

    1992-07-01

    Under contract from the DOE , and in association with CONSOL Inc., Battelle, Pacific Northwest Laboratory (PNL) evaluated four principal and several complementary techniques for the analysis of non-distillable direct coal liquefaction materials in support of process development. Field desorption mass spectrometry (FDMS) and nuclear magnetic resonance (NMR) spectroscopic methods were examined for potential usefulness as techniques to elucidate the chemical structure of residual (nondistillable) direct coal liquefaction derived materials. Supercritical fluid extraction (SFE) and supercritical fluid chromatography/mass spectrometry (SFC/MS) were evaluated for effectiveness in compound-class separation and identification of residual materials. Liquid chromatography (including microcolumn) separation techniques, gas chromatography/mass spectrometry (GC/MS), mass spectrometry/mass spectrometry (MS/MS), and GC/Fourier transform infrared (FTIR) spectroscopy methods were applied to supercritical fluid extracts. The full report authored by the PNL researchers is presented here. The following assessment briefly highlights the major findings of the project, and evaluates the potential of the methods for application to coal liquefaction materials. These results will be incorporated by CONSOL into a general overview of the application of novel analytical techniques to coal-derived materials at the conclusion of CONSOL's contract.

  1. Coal liquefaction with molybdenum catalysts

    SciTech Connect

    Chien, P.L.

    1983-01-01

    Coal liquefaction experiments were carried out in a stirred autoclave under nitrogen. Tetralin was employed as solvent, and the catalyst, when used, was ammonium heptamolybdate (impregnated on coal) or stannous chloride (powdered). Production of pentane soluble oil was higher in the runs with catalyst, but net hydrogen transfer from tetralin to coal was less when catalyst was used. Coal and powdered stannous chloride exhibited a marked synergistic effect on the dehydrogenation of tetralin. A free radical mechanism was suggested to explain this effect, and model experiments with bibenzyl (but no coal) gave results that were consistent with this mechanism. An apparent synergistic effect of coal and impregnated ammonium heptamolybdate was shown to be attributed simply to improved distribution (higher surface area) of the impregnated catalyst, the coal acting as a high-area support. Comparison of the results from autoclave experiments (under nitrogen) with those from tubing bomb experiments (under air) indicated major differences in coal conversion and hydrogen transfer. The conversion was 62% in the autoclave and 81% in the tubing bomb, and the hydrogen transfer was 0.7% in the autoclave and 2.93% in the tubing bomb, when 1% of Mo (based on coal) was impregnated on coal in a preliminary step.

  2. Coal liquefaction with preasphaltene recycle

    DOEpatents

    Weimer, Robert F.; Miller, Robert N.

    1986-01-01

    A coal liquefaction system is disclosed with a novel preasphaltene recycle from a supercritical extraction unit to the slurry mix tank wherein the recycle stream contains at least 90% preasphaltenes (benzene insoluble, pyridine soluble organics) with other residual materials such as unconverted coal and ash. This subject process results in the production of asphaltene materials which can be subjected to hydrotreating to acquire a substitute for No. 6 fuel oil. The preasphaltene-predominant recycle reduces the hydrogen consumption for a process where asphaltene material is being sought.

  3. Coal liquefaction process

    DOEpatents

    Skinner, Ronald W.; Tao, John C.; Znaimer, Samuel

    1985-01-01

    This invention relates to an improved process for the production of liquid carbonaceous fuels and solvents from carbonaceous solid fuels, especially coal. The claimed improved process includes the hydrocracking of the light SRC mixed with a suitable hydrocracker solvent. The recycle of the resulting hydrocracked product, after separation and distillation, is used to produce a solvent for the hydrocracking of the light solvent refined coal.

  4. Coal-derived promoters for the liquefaction of Illinois coal

    SciTech Connect

    Carty, R.H.

    1991-01-01

    The objective of this program is to investigate the use of liquids derived from coal either by mild gasification or supercritical extraction (SCE) to promote direct liquefaction of Illinois coal. Some organic sulfur-, nitrogen-, and oxygen-containing compounds have been found to enhance liquefaction reactions. The use of Illinois coal to produce liquid fractions rich in these types of compounds could increase the rates of liquefaction reactions, thus improving the process economics. An integrated process combining direct liquefaction with mild gasification or SCE of coal is being developed by IGT. The approach taken in this two-year program is to use recently developed molecular probe techniques to assess the reactivity of three coal-derived liquids with respect to (A) hydrogen transfer rate, (B) carbon-carbon bond cleavage rate, (C) free radical flux, and (D) hydrocracking activity. Sample liquids from Illinois Basin Coal IBC-106 are prepared by three methods: mild gasification in an isothermal free-fall reactor (IFFR), steam treatment followed by mild gasification in a fixed-bed reactor (ST/FBR), and SCE using toluene in a batch autoclave. During the first year of the program, the IFFR and ST/FBR coal liquids were produced and characterized, and the IFFR liquid was assessed by the four molecular-probe methods. During the first quarter of the second year, reactivity testing and data analysis on the ST/FBR coal liquid was completed. For the ST/FBR liquid, hydrogen transfer rate showed a mean increase of 7%, C-C bond cleavage selectivity increased by 27%, free radical flux increased 101%, and data indicated a 227% increase in hydrocracking activity. 12 refs., 5 figs., 7 tabs.

  5. EXPLORATORY RESEARCH ON NOVEL COAL LIQUEFACTION CONCEPT

    SciTech Connect

    Brandes, S.D.; Winschel, R.A.

    1998-11-30

    The report presents a summary the work performed under DOE Contract No. DE-AC22-95PC95050. Investigations performed under Task 4--Integrated Flow Sheet Testing are detailed. In this program, a novel direct coal liquefaction technology was investigated by CONSOL Inc. with the University of Kentucky Center for Applied Energy Research and LDP Associates. The process concept explored consists of a first-stage coal dissolution step in which the coal is solubilized by hydride ion donation. In the second stage, the products are catalytically upgraded to refinery feedstocks. Integrated first-stage and solids-separation steps were used to prepare feedstocks for second-stage catalytic upgrading. An engineering and economic evaluation was conducted concurrently with experimental work throughout the program. Approaches to reduce costs for a conceptual commercial plant were recommended at the conclusion of Task 3. These approaches were investigated in Task 4. The economic analysis of the process as it was defined at the conclusion of Task 4, indicates that the production of refined product (gasoline) via this novel direct liquefaction technology is higher than the cost associated with conventional two-stage liquefaction technologies.

  6. Advanced direct coal liquefaction concepts. Quarterly report, October 1, 1993--December 31, 1993

    SciTech Connect

    Berger, D.J.; Parker, R.J.; Simpson, P.L.

    1993-12-31

    Six runs on the bench unit were successfully completed this quarter. The runs covered twenty five different operating conditions and yield periods, and involved 336 hours of operation. In the bench unit, increased temperature of first stage operation (410{degree}C) and direct addition of the powdered solid sodium aluminate to the feed as first stage catalyst improved both coal and carbon monoxide conversion. To achieve 90%+ overall coal conversion, temperatures of 430{degree}C+ were required in the second stage. Oil yields (pentane soluble liquid product) in excess of 65 wt % based on MAF Black Thunder coal, were achieved both with iron oxide/dimethyl disulfide and ammonium molybdate/carbon disulfide second stage catalysts. C{sub l}-C{sub 3} hydrogen gas yields were modest, generally 7-8 wt % on MAF coal, and overall hydrogen consumption (including first stage shift hydrogen) was in the order of 7-8 wt % on MAF coal. The ammonium molybdate catalyst system appeared to give slightly higher oil yields and hydrogen consumption, as was expected, but the differences may not be significant.

  7. Catalytic coal liquefaction process

    DOEpatents

    Garg, D.; Sunder, S.

    1986-12-02

    An improved process for catalytic solvent refining or hydroliquefaction of non-anthracitic coal at elevated temperatures under hydrogen pressure in a solvent comprises using as catalyst a mixture of a 1,2- or 1,4-quinone and an alkaline compound, selected from ammonium, alkali metal, and alkaline earth metal oxides, hydroxides or salts of weak acids. 1 fig.

  8. Catalytic coal liquefaction process

    DOEpatents

    Garg, Diwakar; Sunder, Swaminathan

    1986-01-01

    An improved process for catalytic solvent refining or hydroliquefaction of non-anthracitic coal at elevated temperatures under hydrogen pressure in a solvent comprises using as catalyst a mixture of a 1,2- or 1,4-quinone and an alkaline compound, selected from ammonium, alkali metal, and alkaline earth metal oxides, hydroxides or salts of weak acids.

  9. Cooperative research in coal liquefaction. Final report, May 1, 1990-- April 30, 1991

    SciTech Connect

    Huffman, G.P.

    1992-02-15

    The Consortium for Fossil Fuel Liquefaction Science (CFFLS) is currently engaged in a three year contract with the US Department of Energy investigating a range of research topics dealing with direct coal liquefaction. This report summarizes the results of this program in its second year, from May 1, 1990 to April 30, 1991. Accomplishments for this period are presented for the following tasks: Iron-based catalysts for coal liquefaction, exploratory research on coal conversion, novel coal liquefaction concepts, and novel catalysts for coal liquefaction.

  10. Continuous bench-scale slurry catalyst testing: Direct coal liquefaction of rawhide sub-bituminous coal. Final topical report, June 1994--December 1994

    SciTech Connect

    Coless, L.A.; Poole, M.C.; Wen, M.Y.

    1995-11-21

    Supported catalysts, either in fixed bed or ebullating bed reactors, are subject to deactivation with time, especially if the feed contains deactivating species, such as metals and coke precursors. Dispersed catalyst systems avoid significant catalyst deactivation because there are no catalyst pores to plug, hence no pore mouth plugging, and hopefully, no relevant decline of catalyst surface area or pore volume. The tests carried out in 1994, at the Exxon Research and Development Laboratories (ERDL) for DOE covered a slate of 5 dispersed catalysts for direct coal liquefaction of Rawhide sub-bituminous coal, which is similar to the Black Thunder coal tested earlier at Wilsonville. The catalysts included three iron and two molybdenum types. The Bailey iron oxide and the two molybdenum catalysts have previously been tested in DOE-sponsored research. These known catalysts will be used to help provide a base line and tie-in to previous work. The two new catalysts, Bayferrox PK 5210 and Mach-1`s Nanocat are very finely divided iron oxides. The iron oxide addition rate was varied from 1.0 to 0.25 wt % (dry coal basis) but the molybdenum addition rate remained constant at 100 wppm throughout the experiments. The effect of changing recycle rate, sulfur and iron oxide addition rates, first stage reactor temperature, mass velocity and catalyst type were tested in the 1994 operations of ERDL`s recycle coal liquefaction unit (RCLU). DOE will use these results to update economics and plan future work. The test program will resume in mid 1995, with another 2-3 months of pilot plant testing.

  11. Surfactant studies for coal liquefaction

    SciTech Connect

    Hsu, G.C.

    1990-12-20

    Objectives of this project include: select economical/practical surfactants for use in coal liquefaction; screen surfactants for the proposed work through simple laboratory screening tests; and check the survivability of the selected surfactants at 350{degrees}C and 2000 psi using a 1-hour residence time for the thermal treatment in a stirred autoclave. Surfactant screening studies have shown the lignin sulfonate salt being the best candidate studied. Based upon the findings from the screening studies and practical considerations (e.g., potential cost, thermal survivability and recycling recovery), two surfactant choices in the anionic and nonionic categories were tested further in the autoclave reactor and engineering experiments at JPL. The goal of the autoclave work was to engineering experiments at JPL. The goal of the autoclave work was to determine the effects of surfactants on coal liquefaction performance and to test surfactant survivability. A eight of (8) autoclave experiments using 100 grams of as-received coal were performed. Two commercial surfactant choices were evaluated. They were: Sodium Lignin Sulfonate (LS) as a colloidal (heterogenous) surfactant of anionic type; and Triton X-100 (TRI) (trade name of a polyoxyethylated tert-octyphenol) as a liquid (homogenous) surfactant of nonionic type. Two additional reference tests were performed. 10 refs., 15 figs., 7 tabs.

  12. Preconversion processing of bituminous coals: New directions to improved direct catalytic coal liquefaction. Quarterly report, January 1, 1993--March 31, 1993

    SciTech Connect

    Not Available

    1993-04-01

    The near equal conversions were obtained even with high coal/liquid ratio (1/3--1/2) for two-step wise high-temperature soaking and the first stage liquefaction. Expected conversions were not observed when vacuum distillation after soaking was used in stead of cyclohexane extraction. This is presumably due to the difficulty with redispersion of vacuum distillated bottoms in the coal liquid, because a batch wise procedure was taken by using glasswares. It is suggested that the proposed procedure in the previous quarter should be tested by a continuous procedure under enough heating conditions to keep low viscosity of the bottoms.

  13. Preconversion processing of bituminous coals: New directions to improved direct catalytic coal liquefaction. Quarterly report, September 20, 1991--December 31, 1991

    SciTech Connect

    Not Available

    1992-07-01

    The main task of this quarter was to install reactors to conduct preconversion and liquefaction of coal. Coal and coal liquids were collected. The anaerobic chamber (Model 855-AC; Plas Labs, inc.) was procured and set up to store coal samples under an inert gas. Equipment to treat products was assembled, including Soxhlet extraction units, fractionation columns, a distillation column, and a rotary evaporator. Two gas chromatographs for analysis of gases and liquid were adjusted. Two reactor systems were installed for the experimental apparatus. One was Model 4576 high-temperature and high-pressure autoclave (Parr Instrument, 500{degrees}C and 5000 psi) (see Figure 1); the other was a 27 ml of microreactors. The autoclave was obtained from the manufacturer and assembled. The experimental set-up of microreactors are shown in Figure 2.

  14. Fractionally distilled SRC-I, SRC-II, EDS, H-Coal and ITSL direct coal liquefaction process materials: a comparative summary of chemical analysis and biological testing

    SciTech Connect

    Wright, C.W.; Later, D.W.; Dauble, D.D.; Wilson, B.W.

    1985-07-01

    This document reports and compares the results compiled from chemical analyses and biological testing of coal liquefaction process materials which were fractionally distilled, after production, into various comparable boiling-point range cuts. Comparative analyses were performed on solvent refined coal (SRC)-I, SRC-II, H-Coal, EDS an integrated two-stage liquefaction (ITSL) distillate materials. Mutagenicity and carcinogenicity assays were conducted in conjunction with chromatographic and mass spectrometric analyses to provide detailed, comparative, chemical and biological assessments. Where possible, results obtained from the distillate cuts are compared to those from coal liquefaction materials with limited boiling ranges. Work reported here was conducted by investigators in the Biology and Chemistry Department at the Pacific Northwest Laboratory (PNL), Richland, WA. 38 refs., 16 figs., 27 tabs.

  15. DIRECT LIQUEFACTION PROOF OF CONCEPT

    SciTech Connect

    1998-09-01

    The eighth bench scale test of POC program, Run PB-08, was successfully completed from August 8 to August 26, 1997. A total of five operating conditions were tested aiming at evaluating the reactivity of different pyrolysis oils in liquefaction of a Wyoming sub-bituminous coal (Black Thunder coal). For the first time, water soluble promoters were incorporated into the iron-based GelCat to improve the dispersion of the promoter metals in the feed blend. The concentration of the active metals, Mo and Fe, was 100 and 1000 ppm of moisture-free coal, respectively. Black Thunder coal used in this run was the same batch as tested in HTI�s Run POC-02. Similar to Runs PB-01 through 7, this run employed two back mixed slurry reactors, an interstage gas/slurry separator and a direct-coupled hydrotreater. In addition to the hot vapor from the second stage separator, the first stage separator overhead liquid was also fed to the hydrotreater, which was packed with Criterion C-411 hydrotreating catalyst. Pyrolysis oil was produced off-line from a pyrolysis unit acquired from University of Wyoming. Solids rejection was achieved by purging out pressure filter solid. The recycle solvents consisted of O-6 separator bottoms and pressure filter liquid (PFL). The Run PB-08 proceeded very smoothly without any interruptions. Coal conversion consistently above 90W% was achieved. High resid conversion and distillate yield have been obtained from co-processing of coal and 343°C+ (650°F+) pyrolysis oil. Light gas (C1-C3 ) yield was minimized and hydrogen consumption was reduced due to the introduction of pyrolysis oil, compared with conventional coal-derived solvent. Catalytic activity was improved by incorporating a promoter metal into the iron-based GelCat. It seemed that lowering the first stage temperature to 435°C might increase the hydrogenation function of the promoter metal. In comparison with previous coal-waste coprocessing run (PB-06), significant

  16. Cooperative Research Program in coal liquefaction. Technical report, May 1, 1994--October 31, 1994

    SciTech Connect

    1994-12-31

    Progress reports are presented for the following tasks: coliquefaction of coal with waste materials; catalysts for coal liquefaction to clean transportation fuels; fundamental research in coal liquefaction; and in situ analytical techniques for coal liquefaction and coal liquefaction catalysts.

  17. Cooperative research program in coal liquefaction. Quarterly report, November 1, 1991--January 31, 1992

    SciTech Connect

    Huffman, G.P.

    1992-06-01

    Research continues on coal liquefaction in the following areas: (1) Iron Based Catalysts for Coal Liquefaction; (2) Exploratory Research on Coal Conversion; (3) Novel Coal Liquefaction Concepts; (4) Novel Catalysts for Coal Liquefaction. (VC)

  18. Cooperative research program in coal liquefaction. Quarterly report, August 1, 1991--October 31, 1991

    SciTech Connect

    Huffman, G.P.

    1991-12-31

    This Quarterly Report on coal liquefaction research includes discussion in the areas of (1) Iron Based Catalysts for Coal Liquefaction; (2) Exploratory Research on Coal Conversion; (3) Novel Coal Liquefaction Concepts; (4) Novel Catalysts for Coal Liquefaction. (VC)

  19. Chemical analysis and mutational assay of distilled oils from the H-coal direct liquefaction process: a status report

    SciTech Connect

    Wilson, B.W.; Later, D.W.; Wright, C.W.; Stewart, D.L.

    1985-01-01

    Samples from the H-Coal process, a catalytic, single-stage, coal liquefaction technology, were chemically characterized and screened for microbial mutagenicity. For these investigations, a blend of light and heavy H-Coal process oils was fractionally distilled into 50/sup 0/F boiling point cuts. The chemical analyses and biological testing results presented in this status report deal primarily with the blended material and the distillate fractions boiling above 650/sup 0/F. Results from the microbial mutagenicity assays indicated that onset of biological activity in the crude materials occurred above 700/sup 0/F. Similar trends have been observed for Solvent Refined Coal (SRC) I, SRC II, Integrated Two-Stage Liquefaction (ITSL) and Exxon EDS process materials. After chemical class fractionation, the primary source of microbial mutagenicity of the crude boiling point cuts was the nitrogen-containing polycyclic aromatic compound (N-PAC) fractions. Amino polycyclic aromatic hydrocarbons (amino-PAH) were present at sufficient concentration levels in the N-PAC fractions to account for the observed mutagenic responses. In general, the chemical composition of the H-Coal materials studied was similar to that of other single-stage liquefaction materials. The degree of alkylation in these materials was determined to be greater than in the SRC and less than in the EDS process distillate cuts. 13 references, 8 figures, 11 tables.

  20. Catalytic coal liquefaction. Final report

    SciTech Connect

    Weller, S W

    1981-01-01

    Monolith catalysts of MoO/sub 3/-CoO-Al/sub 2/O/sub 3/ were prepared and tested for coal liquefaction in a stirred autoclave. In general, the monolith catalysts were not as good as particulate catalysts prepared on Corning alumina supports. Measurement of O/sub 2/ chemisorption and BET surface area has been made on a series of Co/Mo/Al/sub 2/O/sub 3/ catalysts obtained from PETC. The catalysts were derived from Cyanamid 1442A and had been tested for coal liquefaction in batch autoclaves and continuous flow units. MoO/sub 3/-Al/sub 2/O/sub 3/ catalysts over the loading range 3.9 to 14.9 wt % MoO/sub 3/ have been studied with respect to BET surface (before and after reduction), O/sub 2/ chemisorption at -78/sup 0/C, redox behavior at 500/sup 0/C, and activity for cyclohexane dehydrogenation at 500/sup 0/C. In connection with the fate of tin catalysts during coal liquefaction, calculations have been made of the relative thermodynamic stability of SnCl/sub 2/, Sn, SnO/sub 2/, and SnS in the presence of H/sub 2/, HCl, H/sub 2/S and H/sub 2/O. Ferrous sulfate dispersed in methylnaphthalene has been shown to be reduced to ferrous sulfide under typical coal hydroliquefaction conditions (1 hour, 450/sup 0/C, 1000 psi initial p/sub H/sub 2//). This suggests that ferrous sulfide may be the common catalytic ingredient when either (a) ferrous sulfate impregnated on powdered coal, or (b) finely divided iron pyrite is used as the catalyst. Old research on impregnated ferrous sulfate, impregnated ferrous halides, and pyrite is consistent with this assumption. Eight Co/Mo/Al/sub 2/O/sub 3/ catalysts from commercial suppliers, along with SnCl/sub 2/, have been studied for the hydrotreating of 1-methylnaphthalene (1-MN) in a stirred autoclave at 450 and 500/sup 0/C.

  1. Fundamental studies of coal liquefaction

    SciTech Connect

    Not Available

    1995-01-01

    The authors have examined the pyrolysis of Argonne samples of Wyodak and Illinois No. 6 coal in argon, undecane, Tetralin, and water. The effects of the pyrolysis on individual particles of coal were monitored visually in a cell with diamond windows capable of operation to temperature and pressures in excess of 500{degrees}C and 3000 psi. The changes in the particles from ambient to 460{degrees}C were recorded in real time on video tape, and images were then taken from the tape record and analyzed. The study showed that in argon both coals developed tars at 350{degrees}-370{degrees}C. The tars then quickly evaporated, leaving core particles remarkably similar in size and shape to the initial particles. These observations suggest that coal does not melt nor become fully liquid when heated. Nor does the softened coal undergo crosslinking to generate coke. Rather the simple loss of volatiles leaves behind the core residue as coke. Contrary to the common view, there appears to be no link between the bond-breaking processes yielding tar and the interaction of the coal with H-donors leading to liquefaction. Water as a medium was surprising in its effect. Both coals began to shrink at 300{degrees}-350{degrees}C, with the effect appearing to be more of an erosion rather than a uniform loss of substance as seen in Tetralin. The Wyodak continued to shrink to 460{degrees}C to about half its initial size. With the Illinois No. 6 coal, however, the process reversed at around 420{degrees}C, and the particles appeared to grow with the evolution of a tar, continuing to 460{degrees}C. The authors submit that this final observation is evidence for hydrothermal synthesis of hydrocarbons at these conditions.

  2. Short contact time direct coal liquefaction using a novel batch reactor. Progress report, September 27, 1993--December 31, 1993

    SciTech Connect

    Klein, M.T.; Calkins, W.H.

    1994-01-19

    The objective for this research is to optimize the design and operation of the bench scale batch reactor (STBR) for coat liquefaction at short contact times (0.01 to 10 minutes). This reactor is simple and low enough in cost to serve as a suitable replacement for the traditional tubing-bomb reactors for coal liquefaction and other high-pressure, high-temperature reaction studies. The details of the reactor system are shown in Figure 2. The heating bath used is a Techne IFB-52 industrial fluidized sand bath, which maintains a reaction temperature of {plus_minus}2{degrees}C. The 30 cm{sup 3} reactor is capable of containing up to 17 MPa (2500 psi) pressure at temperatures up to 550{degrees}C. The tubing used for preheater and precooler was 1/4in. 316 stainless steel with wall thickness of 0.035in. The lengths of the preheater and precooler are selected based on the particular process being studied. Since a gas (e.g. hydrogen or nitrogen) is bubbled through the reaction mixture under pressure and out through a letdown valve, a small water cooled condenser above the reactor before the let-down valve is added to avoid loss of solvent or other low boiling components. Coal liquefaction runs are made by preparing slurries of coal in reagent grade tetralin. Various ratios of tetralin to coal are used, and in some cases, a catalyst such as Ni/Mo on alumina is added.

  3. U.S. DOE indirect coal liquefaction program: An overview

    SciTech Connect

    Shen, J.; Schmetz, E.; Winslow, J.; Tischer, R.; Srivastava, R.

    1997-12-31

    Coal is the most abundant domestic energy resource in the United States. The Fossil Energy Organization within the US Department of Energy (DOE) has been supporting a coal liquefaction program to develop improved technologies to convert coal to clean and cost-effective liquid fuels to complement the dwindling supply of domestic petroleum crude. The goal of this program is to produce coal liquids that are competitive with crude at $20 to $25 per barrel. Indirect and direct liquefaction routes are the two technologies being pursued under the DOE coal liquefaction program. This paper will give an overview of the DOE indirect liquefaction program. More detailed discussions will be given to the F-T diesel and DME fuels which have shown great promises as clean burning alternative diesel fuels. The authors also will briefly discuss the economics of indirect liquefaction and the hurdles and opportunities for the early commercial deployment of these technologies. Discussions will be preceded by two brief reviews on the liquid versus gas phase reactors and the natural gas versus coal based indirect liquefaction.

  4. Hydrogen-donor coal liquefaction process

    DOEpatents

    Wilson, Jr., Edward L.; Mitchell, Willard N.

    1980-01-01

    Improved liquid yields are obtained during the hydrogen-donor solvent liquefaction of coal and similar carbonaceous solids by maintaining a higher concentration of material having hydrogenation catalytic activity in the downstream section of the liquefaction reactor system than in the upstream section of the system.

  5. Solid superacids as coal liquefaction catalysts

    SciTech Connect

    Tierney, J.W.; Wender, I.

    1989-01-01

    Direct coal liquefaction under mild conditions can be achieved by the use of strong acid catalysts. This research is aimed at exploring the possibility of mile coal liquefaction in the presence of solid superacids, especially oxides of iron, titanium, zirconium, and hafnium treated with sulfate ions. Fe{sub 2}O{sub 3}/SO{sub 4}{sup 2{minus}} has been shown to be an impressively active catalyst in coal conversion at 400{degree}C. Our objective is to find conditions under which Fe{sub 2}O{sub 3}/SO{sub 4}{sup 2{minus}} and similar systems catalyze the conversion of coal at mild conditions of temperature and pressure. To date, Fe{sub 2}O{sub 3}/SO{sub 4}{sup 2{minus}}, Ti{sub 2}/SO{sub 4}{sup 2{minus}}, ZrO{sub 2}/SO{sub 4}{sup 2{minus}} catalysts have been synthesized and characterized by XRD, BET, IR, acidity measurement, and sulfur analysis, and a comparison of the relative reactivity of these superacids for n- pentane isomerization and conversion of diphenyl ether and diphenylmethane in both batch and fixed bed reactor systems has been carried out. In this quarter we extended our study of pentane conversion and tested the above catalysts in hydrocracking of longer linear alkanes. We investigated the conversion of coal model compounds including diphenylmethane, dibenyl ether and phenyl benzyl ether at room temperature. We have started work on the conversion of coal at 400{degree}C under hydrogen pressure using an Fe{sub 2}O{sub 3}/SO{sub 4}{sup 2{minus}} catalyst. 3 refs., 3 figs.

  6. Coal liquefaction process streams characterization and evaluation

    SciTech Connect

    Robbins, G.A.; Brandes, S.D.; Winschel, R.A.; Burke, F.P.

    1992-08-01

    This is the tenth Quarterly Technical Progress Report under DOE Contract DE-AC22-89PC89883. Process oils from Wilsonville Run 262 were analyzed to provide information on process performance. Run 262 was operated from July 10 through September 30, 1991, in the thermal/catalytic Close-Coupled Integrated Two-Stage Liquefaction (CC-ITSL) configuration with ash recycle. The feed coal was Black Thunder Mine subbituminous coal. The high/low temperature sequence was used. Each reactor was operated at 50% of the available reactor volume. The interstage separator was in use throughout the run. The second-stage reactor was charged with aged Criterion 324 catalyst (Ni/Mo on 1/16 inch alumina extrudate support). Slurry catalysts and sulfiding agent were fed to the first-stage reactor. Molyvan L is an organometallic compound which contains 8.1% Mo, and is commercially available as an oil-soluble lubricant additive. It was used in Run 262 as a dispersed hydrogenation catalyst precursor, primarily to alleviate deposition problems which plagued past runs with Black Thunder coal. One test was made with little supported catalyst in the second stage. The role of phenolic groups in donor solvent properties was examined. In this study, four samples from direct liquefaction process oils were subjected to O-methylation of the phenolic groups, followed by chemical analysis and solvent quality testing.

  7. Advanced liquefaction using coal swelling and catalyst dispersion techniques

    SciTech Connect

    Curtis, C.W. ); Gutterman, C. ); Chander, S. )

    1992-08-26

    Research in this project centers upon developing a new approach to the direct liquefaction of coal to produce an all-distillate product slate at a sizable cost reduction over current technology. The approach integrates all aspects of the coal liquefaction process including coal selection, pretreatment, coal swelling with catalyst impregnation, coal liquefaction experimentation, product recovery with characterization, alternate bottoms processing, and a technical assessment including an economic evaluation. The project is being carried out under contract to the United States Department of Energy. On May 28, 1992, the Department of Energy authorized starting the experimental aspects of this projects; therefore, experimentation at Amoco started late in this quarterly report period. Research contracts with Auburn University, Pennsylvania State University, and Foster Wheeler Development Corporation were signed during June, 1992, so their work was just getting underway. Their work will be summarized in future quarterly reports. A set of coal samples were sent to Hazen Research for beneficiation. The samples were received and have been analyzed. The literature search covering coal swelling has been up-dated, and preliminary coal swelling experiments were carried out. Further swelling experimentation is underway. An up-date of the literature on the liquefaction of coal using dispersed catalysts is nearing completion; it will be included in the next quarterly report.

  8. Catalyst for coal liquefaction process

    DOEpatents

    Huibers, Derk T. A.; Kang, Chia-Chen C.

    1984-01-01

    An improved catalyst for a coal liquefaction process; e.g., the H-Coal Process, for converting coal into liquid fuels, and where the conversion is carried out in an ebullated-catalyst-bed reactor wherein the coal contacts catalyst particles and is converted, in addition to liquid fuels, to gas and residual oil which includes preasphaltenes and asphaltenes. The improvement comprises a catalyst selected from the group consisting of the oxides of nickel molybdenum, cobalt molybdenum, cobalt tungsten, and nickel tungsten on a carrier of alumina, silica, or a combination of alumina and silica. The catalyst has a total pore volume of about 0.500 to about 0.900 cc/g and the pore volume comprises micropores, intermediate pores and macropores, the surface of the intermediate pores being sufficiently large to convert the preasphaltenes to asphaltenes and lighter molecules. The conversion of the asphaltenes takes place on the surface of micropores. The macropores are for metal deposition and to prevent catalyst agglomeration. The micropores have diameters between about 50 and about 200 angstroms (.ANG.) and comprise from about 50 to about 80% of the pore volume, whereas the intermediate pores have diameters between about 200 and 2000 angstroms (.ANG.) and comprise from about 10 to about 25% of the pore volume, and the macropores have diameters between about 2000 and about 10,000 angstroms (.ANG.) and comprise from about 10 to about 25% of the pore volume. The catalysts are further improved where they contain promoters. Such promoters include the oxides of vanadium, tungsten, copper, iron and barium, tin chloride, tin fluoride and rare earth metals.

  9. Coal-derived promoters for the liquefaction of Illinois coal. [Quarterly] technical report, December 1, 1991--February 29, 1992

    SciTech Connect

    Carty, R.H.; Knight, R.A.

    1992-08-01

    The objective of this program is to investigate the use of liquids derived from coal either by mild gasification or supercritical extraction (SCE) to promote direct liquefaction of Illinois coal. Some organic sulfur-, nitrogen-, and oxygen-containing compounds have been found to enhance liquefaction reactions. The use of Illinois coal to produce liquid fractions rich in these types of compounds could increase the rates of liquefaction reactions, thus improving the process economics. An integrated process combining direct liquefaction with mild gasification or SCE of coal is being developed by IGT.

  10. Advanced direct coal liquefaction concepts. Quarterly report, January 1, 1993--March 31, 1993

    SciTech Connect

    Berger, D.J.; Parker, R.J.; Simpson, P.L.

    1993-07-01

    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 high a severity leads to retrograde reaction and lower coal solubilization. The scope for increasing temperature and time is therefore limited. Petrographic examination of the THF insoluble resids from the autoclave program indicated a maximum coal conversion of about 90% for Black Thunder coal. The bench unit construction was also essentially completed and the bench unit program to be carded out in the next twelve months was defined.

  11. Cooperative research in coal liquefaction infratechnology and generic technology development: Final report, October 1, 1985 to December 31, 1986

    SciTech Connect

    Sendlein, L.V.A.

    1987-06-29

    During the first year of its research program, the Consortium for Fossil Fuel Liquefaction Science has made significant progress in many areas of coal liquefaction and coal structure research. Research topics for which substantial progress has been made include integrated coal structure and liquefaction studies, investigation of differential liquefaction processes, development and application of sophisticated techniques for structural analysis, computer analysis of multivariate data, biodesulfurization of coal, catalysis studies, co-processing of coal and crude oil, coal dissolution and extraction processes, coal depolymerization, determination of the liquefaction characteristics of many US coals for use in a liquefaction database, and completion of a retrospective technology assessment for direct coal liquefaction. These and related topics are discussed in considerably more detail in the remainder of this report. Individual projects are processed separately for the data base.

  12. Experience in feeding coal into a liquefaction process development unit

    NASA Technical Reports Server (NTRS)

    Akhtar, S.; Friedman, S.; Mazzocco, N. J.; Yavorsky, P. M.

    1977-01-01

    A system for preparing coal slurry and feeding it into a high pressure liquefaction plant is described. The system was developed to provide supporting research and development for the Bureau of Mines coal liquefaction pilot plant. Operating experiences are included.

  13. Low Severity Coal Liquefaction Promoted by Cyclic Olefins

    SciTech Connect

    Christine W. Curtis

    1998-04-09

    The development of the donor solvent technology for coal liquefaction has drawn a good deal of attention over the last three decades. The search for better hydrogen donors led investigators to a class of compounds known as cyclic olefins. Cyclic olefins are analogues of the conventional hydroaromatic donor species but do not contain aromatic rings. The cyclic olefins are highly reactive compounds which readily release their hydrogen at temperatures of 200 C or higher. Considerable effort has been o expended toward understanding the process of hydrogen donation. Most of this work was conducted in bomb reactors, with product analysis being carried out after the reaction was complete. Efforts directed towards fundamental studies of these reactions in situ are rare. The current work employs a high temperature and high pressure infrared cell to monitor in situ the concentrations of reactants and products during hydrogen release from hydrogen donor compounds.

  14. EXXON donor solvent coal liquefaction process

    NASA Technical Reports Server (NTRS)

    Epperly, W. R.; Swabb, L. E., Jr.; Tauton, J. W.

    1978-01-01

    A solvent coal liquefaction process to produce low-sulfur liquid products from a wide range of coals is described. An integrated program of laboratory and engineering research and development in conjunction with operation of a 250 T/D pilot plant is discussed.

  15. Coal liquefaction process with enhanced process solvent

    DOEpatents

    Givens, Edwin N.; Kang, Dohee

    1984-01-01

    In an improved coal liquefaction process, including a critical solvent deashing stage, high value product recovery is improved and enhanced process-derived solvent is provided by recycling second separator underflow in the critical solvent deashing stage to the coal slurry mix, for inclusion in the process solvent pool.

  16. Coal liquefaction process research quarterly report, October-December 1979

    SciTech Connect

    Bickel, T.C.; Curlee, R.M.; Granoff, B.; Stohl, F.V.; Thomas, M.G.

    1980-03-01

    This quarterly report summarizes the activities of Sandia's continuing program in coal liquefaction process research. The overall objectives are to: (1) provide a fundamental understanding of the chemistry of coal liquefaction; (2) determine the role of catalysts in coal liquefaction; and (3) determine the mechanism(s) of catalyst deactivation. The program is composed of three major projects: short-contact-time coal liquefaction, mineral effects, and catalyst studies. These projects are interdependent and overlap significantly.

  17. The direct liquefaction proof of concept program

    SciTech Connect

    Comolli, A.G.; Lee, L.K.; Pradhan, V.R.; Stalzer, R.H.

    1995-12-31

    The goal of the Proof of Concept (POC) Program is to develop Direct Coal Liquefaction and associated transitional technologies towards commercial readiness for economically producing premium liquid fuels from coal in an environmentally acceptable manner. The program focuses on developing the two-stage liquefaction (TSL) process by utilizing geographically strategic feedstocks, commercially feasible catalysts, new prototype equipment, and testing co-processing or alternate feedstocks and improved process configurations. Other high priority objectives include dispersed catalyst studies, demonstrating low rank coal liquefaction without solids deposition, improving distillate yields on a unit reactor volume basis, demonstrating ebullated bed operations while obtaining scale-up data, demonstrating optimum catalyst consumption using new concepts (e.g. regeneration, cascading), producing premium products through on-line hydrotreating, demonstrating improved hydrogen utilization for low rank coals using novel heteroatom removal methods, defining and demonstrating two-stage product properties for upgrading; demonstrating efficient and economic solid separation methods, examining the merits of integrated coal cleaning, demonstrating co-processing, studying interactions between the preheater and first and second-stage reactors, improving process operability by testing and incorporating advanced equipment and instrumentation, and demonstrating operation with alternate coal feedstocks. During the past two years major PDU Proof of Concept runs were completed. POC-1 with Illinois No. 6 coal and POC-2 with Black Thunder sub-bituminous coal. Results from these operations are continuing under review and the products are being further refined and upgraded. This paper will update the results from these operations and discuss future plans for the POC program.

  18. Coal liquefaction with subsequent bottoms pyrolysis

    DOEpatents

    Walchuk, George P.

    1978-01-01

    In a coal liquefaction process wherein heavy bottoms produced in a liquefaction zone are upgraded by coking or a similar pyrolysis step, pyrolysis liquids boiling in excess of about 1000.degree. F. are further reacted with molecular hydrogen in a reaction zone external of the liquefaction zone, the resulting effluent is fractionated to produce one or more distillate fractions and a bottoms fraction, a portion of this bottoms fraction is recycled to the reaction zone, and the remaining portion of the bottoms fraction is recycled to the pyrolysis step.

  19. Advanced direct coal liquefaction concepts. Quarterly report, July 1, 1993--September 30, 1993

    SciTech Connect

    Berger, D.J.; Parker, R.J.; Simpson, P.L.

    1993-12-31

    The bench unit was operated in the two stage configuration during this quarter, and two runs (DOE-008 and DOE-009), which included eight mass balance periods were completed. Addition of potassium carbonate, although the best catalyst for promoting the shift reaction in the first stage, led to severe plugging problems particularly between the first and second stage reactors. Therefore, sodium aluminate, less effective as a shift catalyst, but better for unit operation, was used as an alternate. Ammonium tetrathiomolybdate was used throughout as a second stage catalyst, with and without sodium aluminate as shift catalyst. Overall coal conversions under the conditions studied were approximately 80% wt on MAF coal and C{sub 1}--C{sub 4} gas yields were about 10% wt. Conditions in both stages need to be optimized to improve coal conversion and maximize distillable oil yield. The results so far indicate that increased severity and better carbon monoxide shift conversion are required in the first stage, while maximum pressure ({approximately}2,500 psi) is needed in the second stage. The effects of other catalysts also need to be determined, including the establishment of optimum conditions for operation with those catalysts. Ammonium tetrathiomolybdate was shown to possess no measurable activity as a shift catalyst at the level used (600 ppM on total feed) in either the bench unit or autoclave tests. However, in autoclave tests, the addition of ammonium tetrathiomolybdate did improve asphaltene and preasphaltene conversion to oils (and therefore, product quality) in both one and two stage tests when compared with iron sulfide.

  20. Cooperative research program in coal liquefaction. Quarterly report, May 1, 1993--October 31, 1993

    SciTech Connect

    Hoffman, G.P.

    1994-07-01

    This report summarizes progress in four areas of research under the general heading of Coal Liquefaction. Results of studies concerning the coliquefaction of coal with waste organic polymers or chemical products of these polymers were reported. Secondly, studies of catalytic systems for the production of clean transportation fuels from coal were discussed. Thirdly, investigations of the chemical composition of coals and their dehydrogenated counterparts were presented. These studies were directed toward elucidation of coal liquefaction processes on the chemical level. Finally, analytical methodologies developed for in situ monitoring of coal liquefaction were reported. Techniques utilizing model reactions and methods based on XAFS, ESR, and GC/MS are discussed.

  1. Effect of hydrogen pressure on free radicals in direct coal liquefaction/coprocessing

    SciTech Connect

    Seehra, M.S.; Ibrahim, M.M.

    1995-12-31

    The objective of this study was to investigate the coprocessing of coal with waste tires and commingled plastics and to characterize the relevant catalysts, using high pressure/high temperature in-situ ESR (Electron Spin Resonance) spectroscopy. The recent results from high pressure ESR spectroscopy are emphasized. During this period, considerable progress was made in developing the high pressure capabilities in in-situ ESR spectroscopy and new results carried out in 1000 psi of H{sub 2}gas are presented. In these experiments, sapphire tubes were used to contain the high pressures at temperatures up to 500{degrees}C. Results of the experiments carried out under 1000 psi of H{sub 2} are compared with those under 1000 psi of non-interacting argon and with the earlier experiments in flowing H{sub 2} gas where the volatiles are removed by the flowing gas. In these experiments, the free radical density N of the Blind Canyon coal was measured at each temperature and pressure by double integration of the ESR signal and calibrating it against a standard. The details of the experimental apparatus and procedures have been described in earlier publications.

  2. Two-stage, close coupled catalytic liquefaction of coal

    SciTech Connect

    Comolli, A.G.; Johanson, E.S.; Lee, T.L.K.; Popper, G.A.; Stalzer, R.H.

    1992-04-01

    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.

  3. Fired heater for coal liquefaction process

    DOEpatents

    Ying, David H. S.; McDermott, Wayne T.; Givens, Edwin N.

    1985-01-01

    A fired heater for a coal liquefaction process is operated under conditions to maximize the slurry slug frequency and thereby improve the heat transfer efficiency. The operating conditions controlled are (1) the pipe diameter and pipe arrangement, (2) the minimum coal/solvent slurry velocity, (3) the maximum gas superficial velocity, and (4) the range of the volumetric flow velocity ratio of gas to coal/solvent slurry.

  4. Fundamental studies of retrograde reactions in direct liquefaction

    SciTech Connect

    Serio, M.A.; Solomon, P.R.; Bassilakis, R.; Kroo, E.

    1989-01-01

    Most of the proposed processing schemes for improving liquefaction yields involve favoring bond-breaking and radical stabilization reactions over the retrograde reactions. The retrograde reactions are often encountered before liquefaction temperatures are reached. The objective of this program is to elucidate and model the retrograde reaction chemistry in direct coal liquefaction through the application of experimental techniques and theoretical models which have been successfully employed at Advanced Fuel Research (AFR) and SRI International (a subcontractor) to understand and predict coal reaction behavior. The study of retrograde reactions is being done using an integrated approach using extensive characterization of the liquefaction chemistry of three kinds of systems: (1) model polymers; (2) coal; and (3) modified coals.

  5. Polyethylene degradation in a coal liquefaction environment

    SciTech Connect

    Rothenberger, K.S.; Cugini, A.V.; Thompson, R.L.

    1996-12-31

    The coprocessing of coal with waste materials such as plastic has shown promise as an economical means to recover the inherent value of the wastes while producing useful products. Polyethylene (PE) is one of the dominant plastic materials; recent statistics indicate that low- and high-density PE together make up about half of all municipal plastic waste. The degradation of PE in a pyrolysis environment has been well studied, and pyrolysis-based methods for the conversion of PE to fuels have been published. However, recent studies have shown that PE is among the most difficult plastics to convert in the traditional liquefaction environment, particularly in the presence of coal and/or donor solvents. The coal liquefaction environment is quite different than that encountered during thermal or catalytic pyrolysis. Understanding the degradation behavior of PE in the liquefaction environment is important to development of a successful scheme for coprocessing coal with plastics. In this paper, a novel analytical method has been developed to recover incompletely reacted PE from coprocessing product streams. Once separated from the coal-derived material, gel permeation chromatography, a conventional polymer characterization technique, was applied to the recovered material to ascertain the nature of the changes that occurred to the PE upon processing in a bench-scale continuous liquefaction unit. In a separate phase of the project, 1-L semi-batch reactions were performed to investigate the reactivity of PE and coal-PE mixtures as a function of temperature.

  6. Fine particle clay catalysts for coal liquefaction. Final technical report

    SciTech Connect

    Olson, E.S.

    1995-08-01

    In an effort to develop new disposable catalysts for direct coal liquefaction, several types of clay-supported pyrrhotite catalysts were prepared and tested. These included iron-pillared montmorillonite, mixed iron/alumina-pillared montmorillonite, iron-impregnated montmorillonite, and iron oxometallate-impregnated montmorillonite.

  7. Liquefaction Of Coal With Surfactant And Disposable Catalyst

    NASA Technical Reports Server (NTRS)

    Hickey, Gregory S.; Sharma, Pramod K.

    1996-01-01

    Fuels derived from coal more competitive with petroleum products. Improved coal-liquefaction process exploits synergistic effects of disposable iron oxide catalyst and cheap anionic surfactant. Efficiency of conversion achieved in significantly higher than efficiencies obtained with addition of either surfactant or catalyst alone. No costly pretreatment necessary, and increase in conversion achieved under processing conditions milder than those used heretofore in liquefaction of coal. Quality of distillates obtained after liquefaction in process expected superior to distillates obtained after liquefaction by older techniques.

  8. Catalytic direct liquefaction of high-sulfur coals and their blends with asphaltite in the absence of a solvent

    SciTech Connect

    Omer Gul; Parvana Gafarova; Arif Hesenov; Harold H. Schobert; Oktay Erbatur

    2007-08-15

    Two high-sulfur Turkish coals (Mengen and Kangal) and an asphaltite (Avgamasya) were liquefied with and without the catalyst precursors ammonium heptamolybdate (AHM) and ammonium tetrathiomolybdate (ATTM) at 300, 350, 400, and 450{sup o}C. Blends of these coals with the asphaltite were also liquefied using ATTM. Effective conversions of both coals into oils and into asphaltene and preasphaltene fractions were achieved with both catalyst precursors, although ATTM was more effective than AHM. Maximum conversion for Mengen coal with ATTM (89.2%) was achieved at 400{sup o}C, although the maximum yield of oils (56.9%) was obtained at 450{sup o}C. Kangal, in the presence of ATTM, gave maximum conversion (87.7%) at 400{sup o}C; the corresponding oil yield (49.6%) was not much less than that obtained at 450{sup o}C (49.9%). Some retrogressive reactions toward the formation of aromatics were observed during liquefaction at 450{sup o}C in the presence of AHM or ATTM with both coals. Also, using these catalyst precursors results in effective hydrogenation of two-ring or higher condensed aromatics and effective hydrogenolysis of the alicyclic part of hydroaromatic structures. On the other hand, these catalyst precursors do not provide effective saturation of monoaromatic rings, although the use of ATTM yielded partial reduction of these compounds. The distribution of main product fractions obtained from these reactions and the detailed analysis of oils obtained are reported. 118 refs., 4 figs., 15 tabs.

  9. Impact of hydrodynamics on coal liquefaction. Final technical report

    SciTech Connect

    Kang, D.; Ying, D.H.S.; Givens, E.N.

    1983-09-01

    We have attempted to determine the hydrodynamic effects of various reactor configurations on coal liquefaction, to help select the optimal reactor configuration and to provide additional understanding of coal liquefaction reaction kinetics, which cannot be definitively determined by a CSTR alone. Only a qualitative understanding of the fluid dynamic effects on product yields has been perceived by operating various sizes of open-column tubular reactors, because the fluid-dynamic characteristics of these reactors were not clearly understood and could not be varied significantly. Indirect studies, by cold-flow simulation, have been of little help in defining the fluid dynamic impact on coal liquefaction. Comparison of actual coal liquefaction data from both the plug-flow reactor and the CSTR showed that the plug-flow configuration had various advantages. Reactor yields improved significantly, especially the primary product conversions. At 840/sup 0/F and residence times of 29 and 40 min, coal and preasphaltene conversions were enhanced approximately 6 and 10%, respectively. At these conditions, the plug-flow reactor also yielded about 10% more oils than the CSTR with significant increase in hydrogen utilization. Also, this study provided an opportunity to examine the soundness of APCI/ICRC's sequential kinetic model, by interfacing the plug-flow and CSTR yield data. Transforming CSTR yields to plug-flow data showed that product yields deviated considerably from the measured plug-flow data, suggesting the need to improve the existing reaction model. Having both CSTR and plug-flow reactor data bases is important for developing a sound coal reaction model and for determining hydrodynamic effects on coal liquefaction in a direct way. The results will lead to an optimized reactor configuration as well as optimized operation. 5 references, 23 figures, 20 tables.

  10. Integrated coal cleaning, liquefaction, and gasification process

    DOEpatents

    Chervenak, Michael C.

    1980-01-01

    Coal is finely ground and cleaned so as to preferentially remove denser ash-containing particles along with some coal. The resulting cleaned coal portion having reduced ash content is then fed to a coal hydrogenation system for the production of desirable hydrocarbon gases and liquid products. The remaining ash-enriched coal portion is gasified to produce a synthesis gas, the ash is removed from the gasifier usually as slag, and the synthesis gas is shift converted with steam and purified to produce the high purity hydrogen needed in the coal hydrogenation system. This overall process increases the utilization of as-mined coal, reduces the problems associated with ash in the liquefaction-hydrogenation system, and permits a desirable simplification of a liquids-solids separation step otherwise required in the coal hydrogenation system.

  11. Fired heater for coal liquefaction process

    DOEpatents

    Ying, David H. S.

    1984-01-01

    A fired heater for a coal liquefaction process is constructed with a heat transfer tube having U-bends at regular intervals along the length thereof to increase the slug frequency of the multi-phase mixture flowing therethrough to thereby improve the heat transfer efficiency.

  12. Process for coal liquefaction employing selective coal feed

    DOEpatents

    Hoover, David S.; Givens, Edwin N.

    1983-01-01

    An improved coal liquefaction process is provided whereby coal conversion is improved and yields of pentane soluble liquefaction products are increased. In this process, selected feed coal is pulverized and slurried with a process derived solvent, passed through a preheater and one or more dissolvers in the presence of hydrogen-rich gases at elevated temperatures and pressures, following which solids, including mineral ash and unconverted coal macerals, are separated from the condensed reactor effluent. The selected feed coals comprise washed coals having a substantial amount of mineral matter, preferably from about 25-75%, by weight, based upon run-of-mine coal, removed with at least 1.0% by weight of pyritic sulfur remaining and exhibiting vitrinite reflectance of less than about 0.70%.

  13. A Characterization and Evaluation of Coal Liquefaction Process Streams The Kinetics of Coal Liquefaction Distillation Resid Conversion

    SciTech Connect

    D.Campbell; D.G. Nichols; D.J. Pazuchanics; H.Huang; M.T.Klein; R.A. Winschel; S.D. Brandes; S.Wang; W.H. Calkins

    1998-06-04

    Under subcontract from CONSOL Inc. (DOE Contract N o. DE- AC22- 94PC93054), the University of Delaware studied the mechanism and kinetics of coal liquefaction resid conversion. Th e program at Delaware was conducted be tween 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 reactivit y 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 th e project authored by CONSOL and a report of the program findings authored by the University of Delaware researchers are presented here. INTRODUCTION Resid hydrocracking is a key reaction of modern (i. e., distillate- producing) coal liquefactio n processes. Coals are readily converted to resid a nd lighter products in the liquefaction process. The resid is combined with fr esh coal in a ratio often greater than 1: 1, and some vacuum gas oil and is recycled to be further converted. Understanding the chemistry of resids and resi d reactivity is important to improve direct liquefaction process design and to achieve economi c objectives for direct coal liquefaction. Computational models that predict resid conversion from the chemical characteristics of the resids and reaction conditions would be a cost- efficient way to explore process variables. Implementation of such models could aid in the design an d operation of liquefaction facilities.

  14. Two-stage coal liquefaction process

    DOEpatents

    Skinner, Ronald W.; Tao, John C.; Znaimer, Samuel

    1985-01-01

    An improved SRC-I two-stage coal liquefaction process which improves the product slate is provided. Substantially all of the net yield of 650.degree.-850.degree. F. heavy distillate from the LC-Finer is combined with the SRC process solvent, substantially all of the net 400.degree.-650.degree. F. middle distillate from the SRC section is combined with the hydrocracker solvent in the LC-Finer, and the initial boiling point of the SRC process solvent is increased sufficiently high to produce a net yield of 650.degree.-850.degree. F. heavy distillate of zero for the two-stage liquefaction process.

  15. Optimization of reactor configuration in coal liquefaction

    SciTech Connect

    Comolli, A.G.; Johanson, E.S.; Lee, L.K.; Stalzer, R.M.

    1992-12-01

    This quarterly report covers activities of optimization of Reactor Configuration in Coal Liquefaction during the period July 1--September 30, 1992, at Hydrocarbon Research, Inc. in Lawrenceville and Princeton, New Jersey. This DOE contract period is from October 1, 1991 to September 30, 1993. The overall objective of the program is to achieve a new approach to liquefaction that generates an all distillates product slate at reduced cost of about $25 per barrel of crude oil equivalent. The quarterly report covers work on Laboratory Support, Laboratory Scale Operations, Technical Assessment, and Project Management.

  16. Pillared montmorillonite catalysts for coal liquefaction

    SciTech Connect

    Sharma, R.K.; Olson, E.S.

    1994-12-31

    Pillared clays contain large micropores and have considerable potential for catalytic hydrogenation and cleavage of coal macromolecules. Pillared montmorillonite-supported catalysts were prepared by the intercalation of polynuclear hydroxychromium cations and subsequent impregnation of nickel and molybdenum. Infrared and thermogravimetric studies of pyridine-adsorbed catalysts indicated the presence of both Lewis and Bronsted acid sites. Thus, the catalysts have both acidic properties that can aid in hydrocracking and cleavage of carbon-heteroatom bonds as well as hydrogen-activating bimetallic sites. These catalysts were applied to the hydrodesulfurization and liquefaction of coal-derived intermediates. The reactions of model organosulfur compounds and coal liquids were carried out at 300{degrees}-400{degrees}C for 3 hours in the presence of 1000 psi of molecular hydrogen. Reaction products were analyzed by GC/FT-IR/MS/AED. The catalysts have been found to be very effective in removing sulfur from model compounds as well as liquefaction products.

  17. Polyethylene degradation in a coal liquefaction environment

    SciTech Connect

    Thompson, R.L.; Rothenberger, K.S.; Cugini, A.V.

    1996-12-31

    The coprocessing of coal with waste materials such as plastic has shown promise as an economical means to recover the inherent value of the wastes while producing useful products. Polyethylene (PE) is one of the dominant plastics on the market; recent statistics indicate that low- and high-density PE together make up about half of all municipal plastic waste. However, recent studies have shown that PE is also among the most difficult plastics to convert in the traditional liquefaction environment, particularly in the presence of coal and/or donor solvents. The coal liquefaction environment is quite different than that encountered during thermal or catalytic pyrolysis. In this paper, a novel analytical method has been developed to recover incompletely reacted PE from coprocessing product streams. Once separated from the coal-derived material, gel permeation chromatography (GPC) was applied to the recovered material to ascertain the nature of the changes that occurred to the PE upon processing in a bench-scale continuous liquefaction unit. Also, 1-L semi-batch reactions were performed to investigate the reactivity of PE and coal-PE mixtures as a function of temperature.

  18. Technology for advanced liquefaction processes: Coal/waste coprocessing studies

    SciTech Connect

    Cugini, A.V.; Rothenberger, K.S.; Ciocco, M.V.

    1995-12-31

    The efforts in this project are directed toward three areas: (1) novel catalyst (supported and unsupported) research and development, (2) study and optimization of major operating parameters (specifically pressure), and (3) coal/waste coprocessing. The novel catalyst research and development activity has involved testing supported catalysts, dispersed catalysts, and use of catalyst testing units to investigate the effects of operating parameters (the second area) with both supported and unsupported catalysts. Several supported catalysts were tested in a simulated first stage coal liquefaction application at 404{degrees}C during this performance period. A Ni-Mo hydrous titanate catalyst on an Amocat support prepared by Sandia National laboratories was tested. Other baseline experiments using AO-60 and Amocat, both Ni-Mo/Al{sub 2}O{sub 3} supported catalysts, were also made. These experiments were short duration (approximately 12 days) and monitored the initial activity of the catalysts. The results of these tests indicate that the Sandia catalyst performed as well as the commercially prepared catalysts. Future tests are planned with other Sandia preparations. The dispersed catalysts tested include sulfated iron oxide, Bayferrox iron oxide (iron oxide from Miles, Inc.), and Bailey iron oxide (micronized iron oxide from Bailey, Inc.). The effects of space velocity, temperature, and solvent-to-coal ratio on coal liquefaction activity with the dispersed catalysts were investigated. A comparison of the coal liquefaction activity of these catalysts relative to iron catalysts tested earlier, including FeOOH-impregnated coal, was made. These studies are discussed.

  19. Effects of coal rank on the chemical composition and toxicological activity of coal liquefaction materials

    SciTech Connect

    Wright, C.W.; Dauble, D.D.

    1986-05-01

    This report presents data from the chemical analysis and toxicological testing of coal liquefaction materials from the EDS and H-Coal processes operated using different ranks of coal. Samples of recycle solvent from the bottoms recycle mode of the EDS direct coal liquefaction process derived from bituminous, sub-bituminous, and lignite coals were analyzed. In addition, the H-Coal heavy fuel oils derived from bituminous and sub-bituminous coals were analyzed. Chemical methods of analysis included adsoprtion column chromatography, high-resolution gas chromatography, gas chromatography/mass spectrometry, and low-voltage probe-inlet mass spectrometry. The toxicological activity of selected samples was evaluated using the standard microbial mutagenicity assay, an initiation/promotion assay for mouse-skin tumorigenicity, and a static bioassy with Daphnia magna for aquatic toxicity of the water-soluble fractions. 22 refs., 16 figs., 14 tabs.

  20. Coal liquefaction process streams characterization and evaluation:

    SciTech Connect

    Malhotra, R.; McMillen, D.F. ); Burke, F.P.; Winschel, R.A.; Brandes, S.D. . Research and Development Dept.)

    1992-01-01

    SRI International evaluated two analytical methods for application to coal liquefaction. These included field ionization mass spectrometry and a technique employing iodotrimethylsilane for the derivatization of oxygen bound to alkyl carbon (alkyl ethers). The full report authored by the SRI researchers is presented here. The following assessment briefly highlights the major findings of the project, and evaluates the potential of the methods for application to coal-derived materials. These results will be incorporated by Consol into a general overview of the application of novel analytical techniques to coal-derived materials at the conclusion of this contract. (VC)

  1. Free-radical kinetics of coal liquefaction

    SciTech Connect

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

    1994-07-16

    A rate expression with first- and second-order terms in the concentration of extractable compounds in solid coal particles is derived from a fundamental free-radical mechanism. The expression was suggested empirically by prior experiments for coal liquefaction in the presence of a hydrogen-donor solvent. Radical reactions are considered to occur in both coal and in solvent. The long-chain approximation justifies the neglect of initiation, hydrogen abstraction, and termination rates as quantitatively insignificant relative to propagation reaction rates.

  2. Coal liquefaction process streams characterization and evaluation. Quarterly technical progress report, April 1--June 30, 1991

    SciTech Connect

    Robbins, G.A.; Brandes, S.D.; Winschel, R.A.; Burke, F.P.

    1991-11-01

    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.

  3. Coal liquefaction process streams characterization and evaluation. Quarterly technical progresss report, January 1--March 31, 1991

    SciTech Connect

    Brandes, S.D.; Winschel, R.A.; Burke, F.P.; Robbins, G.A.

    1991-09-01

    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.

  4. Coal liquefaction process streams characterization and evaluation. Quarterly technical progress report, October 1--December 31, 1991

    SciTech Connect

    Robbins, G.A.; Brandes, S.D.; Winschel, R.A.; Burke, F.P.

    1992-03-01

    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.

  5. Prevention of deleterious deposits in a coal liquefaction system

    DOEpatents

    Carr, Norman L.; Prudich, Michael E.; King, Jr., William E.; Moon, William G.

    1984-07-03

    A process for preventing the formation of deleterious coke deposits on the walls of coal liquefaction reactor vessels involves passing hydrogen and a feed slurry comprising feed coal and recycle liquid solvent to a coal liquefaction reaction zone while imparting a critical mixing energy of at least 3500 ergs per cubic centimeter of reaction zone volume per second to the reacting slurry.

  6. A characterization and evaluation of coal liquefaction process streams. Quarterly technical progress report, April 1--June 30, 1996

    SciTech Connect

    Robbins, G.A.; Brandes, S.D.; Winschel, R.A.

    1997-03-01

    The objectives of this project are to support the DOE direct coal liquefaction process development program and to improve the useful application of chemical analyses to direct coal liquefaction process development. Independent analyses by well-established methods are obtained of samples produced in direct coal liquefaction processes under evaluation by DOE. Additionally, new analytical instruments and techniques to examine coal-derived samples are being evaluated. The data obtained form this study are used to guide 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 experimental data, a kinetic model of resid conversion will be constructed. Such a model will provide insights to improve process performance and the economics of direct coal liquefaction.

  7. Direct liquefaction proof-of-concept facility

    SciTech Connect

    Alfred G. Comolli; Peizheng Zhou; HTI Staff

    2000-01-01

    The main objective of the U.S. DOE, Office of Fossil Energy, is to ensure the US a secure energy supply at an affordable price. An integral part of this program was the demonstration of fully developed coal liquefaction processes that could be implemented if market and supply considerations so required, Demonstration of the technology, even if not commercialized, provides a security factor for the country if it is known that the coal to liquid processes are proven and readily available. Direct liquefaction breaks down and rearranges complex hydrocarbon molecules from coal, adds hydrogen, and cracks the large molecules to those in the fuel range, removes hetero-atoms and gives the liquids characteristics comparable to petroleum derived fuels. The current processes being scaled and demonstrated are based on two reactor stages that increase conversion efficiency and improve quality by providing the flexibility to adjust process conditions to accommodate favorable reactions. The first stage conditions promote hydrogenation and some oxygen, sulfur and nitrogen removal. The second stage hydrocracks and speeds the conversion to liquids while removing the remaining sulfur and nitrogen. A third hydrotreatment stage can be used to upgrade the liquids to clean specification fuels.

  8. Hydrogen donor solvent coal liquefaction process

    DOEpatents

    Plumlee, Karl W.

    1978-01-01

    An indigenous hydrocarbon product stream boiling within a range of from about C.sub.1 -700.degree. F., preferably C.sub.1 -400.degree. F., is treated to produce an upgraded hydrocarbon fuel component and a component which can be recycled, with a suitable donor solvent, to a coal liquefaction zone to catalyze the reaction. In accordance therewith, a liquid hydrocarbon fraction with a high end boiling point range up to about 700.degree. F., preferably up to about 400.degree. F., is separated from a coal liquefaction zone effluent, the separated fraction is contacted with an alkaline medium to provide a hydrocarbon phase and an aqueous extract phase, the aqueous phase is neutralized, and contacted with a peroxygen compound to convert indigenous components of the aqueous phase of said hydrocarbon fraction into catalytic components, such that the aqueous stream is suitable for recycle to the coal liquefaction zone. Naturally occurring phenols and alkyl substituted phenols, found in the aqueous phase, are converted, by the addition of hydroxyl constituents to phenols, to dihydroxy benzenes which, as disclosed in copending Application Ser. Nos. 686,813 now U.S. Pat. No. 4,049,536; 686,814 now U.S. Pat. No. 4,049,537; 686,827 now U.S. Pat. No. 4,051,012 and 686,828, K. W. Plumlee et al, filed May 17, 1976, are suitable hydrogen transfer catalysts.

  9. CAMD studies of coal structure and coal liquefaction

    SciTech Connect

    Faulon, J.L.; Carlson, G.A.

    1994-10-01

    The macromolecular structure of coal is essential to understand the mechanisms occurring during coal liquefaction. Many attempts to model coal structure can be found in the literature. More specifically for high volatile bituminous coal, the subject of interest the most commonly quoted models are the models of Given, Wiser, Solomon, and Shinn. In past work, the authors`s have used computer-aided molecular design (CAMD) to develop three-dimensional representations for the above coal models. The three-dimensional structures were energy minimized using molecular mechanics and molecular dynamics. True density and micopore volume were evaluated for each model. With the exception of Given`s model, the computed density values were found to be in agreement with the corresponding experimental results. The above coal models were constructed by a trial and error technique consisting of a manual fitting of the-analytical data. It is obvious that for each model the amount of data is small compared to the actual complexity of coal, and for all of the models more than one structure can be built. Hence, the process by which one structure is chosen instead of another is not clear. In fact, all the authors agree that the structure they derived was only intended to represent an {open_quotes}average{close_quotes} coal model rather than a unique correct structure. The purpose of this program is further develop CAMD techniques to increase the understanding of coal structure and its relationship to coal liquefaction.

  10. Coal liquefaction with preasphaltene recycle

    SciTech Connect

    Weimer, R.F.; Miller, R.N.

    1986-09-02

    A process is described for solvent refining coal to yield an asphaltene-rich product stream by forming a slurry of finely divided coal and a process solvent therefor, which process comprises the steps of: (1) contacting the slurry with a hydrogen-rich gas; (2) heating the slurry in the presence of the hydrogen-rich gas. (3) permitting the heated slurry to react and to dissolve at least some of the coal. (4) adding fresh hydrogen as required to form a liquefied coal slurry; (5) passing the liquefied coal slurry to a separator in which a vapor product stream and a condensed product stream are separated; (6) passing the condensed product stream to a vacuum distillation still; (7) removing from the vacuum distillation still a residual bottoms product, wherein the residual bottoms product from the still is mixed with a suitable extractions solvent and is passed to supercritical extraction system to separate an asphaltene-rich stream comprised of pentane solubles and benzene solubles from a preasphaltene-rich stream which includes solids residue material, the preasphaltene-rich stream comprised of benzene insolubles, pyridine solubles, pyridine insolubles and ash; (8) recycling at least a portion of the preasphaltene-rich stream together with the solid residue material as process solvent, with less than 10 percent of the process solvent comprising asphaltenes; (9) withdrawing the asphaltene-rich stream and passing the asphaltene-rich stream to a solvent recovery system to yield an asphaltene-rich product stream and an extraction solvent stream.

  11. Two-stage coal liquefaction without gas-phase hydrogen

    DOEpatents

    Stephens, H.P.

    1986-06-05

    A process is provided for the production of a hydrogen-donor solvent useful in the liquefaction of coal, wherein the water-gas shift reaction is used to produce hydrogen while simultaneously hydrogenating a donor solvent. A process for the liquefaction of coal using said solvent is also provided. The process enables avoiding the use of a separate water-gas shift reactor as well as high pressure equipment for liquefaction. 3 tabs.

  12. One-Step Coal Liquefaction

    NASA Technical Reports Server (NTRS)

    Qader, S. A.

    1984-01-01

    Steam injection improves yield and quality of product. Single step process for liquefying coal increases liquid yield and reduces hydrogen consumption. Principal difference between this and earlier processes includes injection of steam into reactor. Steam lowers viscosity of liquid product, so further upgrading unnecessary.

  13. Catalysts for coal liquefaction processes

    DOEpatents

    Garg, Diwakar

    1986-01-01

    Improved catalysts for catalytic solvent refining or hydroliquefaction of non-anthracitic coal at elevated temperatures under hydrogen pressure in a hydrogen donor solvent comprise a combination of zinc or copper, or a compound thereof, and a Group VI or non-ferrous Group VIII metal, or a compound thereof.

  14. Catalysts for coal liquefaction processes

    DOEpatents

    Garg, D.

    1986-10-14

    Improved catalysts for catalytic solvent refining or hydroliquefaction of non-anthracitic coal at elevated temperatures under hydrogen pressure in a hydrogen donor solvent comprise a combination of zinc or copper, or a compound thereof, and a Group VI or non-ferrous Group VIII metal, or a compound thereof.

  15. Process for coal liquefaction in staged dissolvers

    DOEpatents

    Roberts, George W.; Givens, Edwin N.; Skinner, Ronald W.

    1983-01-01

    There is described an improved liquefaction process by which coal is converted to a low ash and low sulfur carbonaceous material that can be used as a fuel in an environmentally acceptable manner without costly gas scrubbing equipment. In the process, coal is slurried with a pasting oil, passed through a preheater and at least two dissolvers in series in the presence of hydrogen-rich gases at elevated temperatures and pressures. Solids, including mineral ash and unconverted coal macerals, are separated from the condensed reactor effluent. In accordance with the improved process, the first dissolver is operated at a higher temperature than the second dissolver. This temperature sequence produces improved product selectivity and permits the incorporation of sufficient hydrogen in the solvent for adequate recycle operations.

  16. Coal liquefaction: A research and development needs assessment: Final report, Volume I

    SciTech Connect

    Schindler, H.D.; Burke, F.P.; Chao, K.C.; Davis, B.H.; Gorbaty, M.L.; Klier, K.; Kruse, C.W.; Larsen, J.W.; Lumpkin, R.E.; McIlwain, M.E.; Wender, I.; Stewart, N.

    1989-03-01

    The DOE Coal Liquefaction Research Needs (COLIRN) Panel reviewed, developed, and assessed R and D needs for the development of coal liquefaction for the production of transportation fuels. Technical, economics, and environmental considerations were important components of the panel's deliberations. The panel examined in some depth each of the following technologies: direct liquefaction of coal, indirect liquefaction via conversion of coal-derived synthesis gas, pyrolysis, coprocessing of combined coal/oil feedstocks, and bioconversion of coal and coal-derived materials. In this assessment particular attention was given to highlighting the fundamental and applied research which has revealed new and improved liquefaction mechanisms, the potentially promising innovative processes currently emerging, and the technological and engineering improvements necessary for significant cost reductions. As the result of this assessment, the COLIRN panel developed a list of prioritized research recommendations needed to bring coal liquefaction to technical and economic readiness in the next 5--20 years. The findings and the research recommendations generated by the COLIRN panel are summarized in this publication. 107 figs., 63 tabs.

  17. Coal liquefaction laboratory studies. Volume 1. Two-stage variations - bituminous coal

    SciTech Connect

    Bynum, R.; Carver, J.M.; Gir, S.; Paranjape, A.S.; Rhodes, D.E.

    1985-07-01

    Laboratory studies were conducted to provide guidance in the selection of process variable levels for the Liquefaction-section of the continuous coal liquefaction bench-scale unit operated at Kerr-McGee Cimarron Facility. Using the results of batch reactor tests made with Illinois No. 6 coal, an empirical correlation was developed to predict the distillate yield from a thermal-liquefaction at 825/sup 0/F reaction-temperature as a linear function of the reaction-time, recycle resid to MAF coal ratio and the initial hydrogen pressure. Several single-ring and multi-ring organonitrogen compounds were evaluated as liquefaction solvents. Data indicate that basic organonitrogen compounds, saturated or partially saturated, have a more pronounced effect on the conversion results and particularly on toluene-soluble coal conversions, thereby suggesting that the primary driving force for good conversions may be the unshared pair of electrons associated with the nitrogen atom in these compounds. A study of microautoclaves indicated that sufficient mixing of the contents is necessary to obtain good conversions. The THF-soluble coal conversions were studied as a function of the hydrogen donor concentration in the liquid phase. Variations in product work-up procedures could result in significant differences in the observed THF-soluble and/or toluene-soluble results. A direct comparison of data from different sources should be done with caution and should take into consideration the differences between the equipment and product work-up procedures used. 17 figs., 73 tabs.

  18. Coal liquefaction process with increased naphtha yields

    DOEpatents

    Ryan, Daniel F.

    1986-01-01

    An improved process for liquefying solid carbonaceous materials wherein the solid carbonaceous material is slurried with a suitable solvent and then subjected to liquefaction at elevated temperature and pressure to produce a normally gaseous product, a normally liquid product and a normally solid product. The normally liquid product is further separated into a naphtha boiling range product, a solvent boiling range product and a vacuum gas-oil boiling range product. At least a portion of the solvent boiling-range product and the vacuum gas-oil boiling range product are then combined and passed to a hydrotreater where the mixture is hydrotreated at relatively severe hydrotreating conditions and the liquid product from the hydrotreater then passed to a catalytic cracker. In the catalytic cracker, the hydrotreater effluent is converted partially to a naphtha boiling range product and to a solvent boiling range product. The naphtha boiling range product is added to the naphtha boiling range product from coal liquefaction to thereby significantly increase the production of naphtha boiling range materials. At least a portion of the solvent boiling range product, on the other hand, is separately hydrogenated and used as solvent for the liquefaction. Use of this material as at least a portion of the solvent significantly reduces the amount of saturated materials in said solvent.

  19. Coal liquefaction process streams characterization and evaluation: Analysis of coal-derived synthetic crude from HRI CTSL Run CC-15 and HRI Run CMSL-2

    SciTech Connect

    Sturm, G.P. Jr.; Kim, J.; Shay, J.

    1994-01-01

    Under subcontract from CONSOL Inc. (US DOE Contract No. DE-AC22-89PC89883), IIT Research Institute, National Institute for Petroleum and Energy Research applied a suite of petroleum inspection tests to two direct coal liquefactions net product oils produced in two direct coal liquefaction processing runs. Two technical reports, authored by NIPER, are presented here. The following assessment briefly describes the two coal liquefaction runs and highlights the major findings of the project. It generally is concluded that the methods used in these studies can help define the value of liquefaction products and the requirements for further processing. The application of these methods adds substantially to our understanding of the coal liquefaction process and the chemistry of coal-derived materials. These results will be incorporated by CONSOL into a general overview of the application of novel analytical techniques to coal-derived materials at the conclusion of this contract.

  20. Liquefaction of calcium-containing subbituminous coals and coals of lower rank

    DOEpatents

    Brunson, Roy J.

    1979-01-01

    An improved process for the treatment of a calcium-containing subbituminous coal and coals of lower rank to form insoluble, thermally stable calcium salts which remain within the solids portions of the residue on liquefaction of the coal, thereby suppressing the formation of scale, made up largely of calcium carbonate which normally forms within the coal liquefaction reactor (i.e., coal liquefaction zone), e.g., on reactor surfaces, lines, auxiliary equipment and the like. An oxide of sulfur, in liquid phase, is contacted with a coal feed sufficient to impregnate the pores of the coal. The impregnated coal, in particulate form, can thereafter be liquefied in a coal liquefaction reactor (reaction zone) at coal liquefaction conditions without significant formation of scale.

  1. Coal liquefaction process streams characterization and evaluation: The preliminary evaluation of the kinetics of coal liquefaction distillation resid conversion

    SciTech Connect

    Klein, M.T.; Calkins, W.H.; Huang, He

    1994-02-01

    This study evaluated the use of a novel laboratory-scale batch reactor, designed by the University of Delaware, to study the kinetics of coal liquefaction resid reactivity. The short time batch reactor (STBR) is capable of conducting reactions at temperatures up to 450{degrees}C and pressures up to 2500 psi at well-defined reaction times from a few seconds to 30 min or longer. Sixty experiments were conducted with the STBR in this project. The products of the resid/tetralin/hydrogen reaction were separated by solubility, and several analytical procedures were used to evaluate the reaction products, including thermogravimetric analysis (TGA), gas chromatography (GC) and gas chromatography/mass spectrometry (GC/MS). Changes were monitored in the boiling ranges of the products, as a function of process conditions (time, temperature, and tetralin donor solvent-to-resid ratio), with and without catalysts. Two distillation resid samples were studied; Sample 1 is the resid of the second stage product stream from Wilsonville Run 259 which used Pittsburgh seam coal (Ireland mine) bituminous coal, and Sample 2 is the resid of the same streak from Wilsonville Run 260 which used Wyodak and Anderson (Black Thunder Mine) subbituminous coal. It was determined that the resid reactivity was different for the two samples studied. The results demonstrate that further development of this experimental method is warranted to empirically assess resid reactivity and to provide data for use in the construction of an empirical model of coal conversion in the direct liquefaction process.

  2. Coal liquefaction process streams characterization and evaluation. Volume 1, Base program activities

    SciTech Connect

    Robbins, G.A.; Brandes, S.D.; Winschel, R.A.; Burke, F.P.

    1994-05-01

    This 4.5-year project consisted of routine analytical support to DOE`s direct liquefaction process development effort (the Base Program), and an extensive effort to develop, demonstrate, and apply new analytical methods for the characterization of liquefaction process streams (the Participants Program). The objective of the Base Program was to support the on-going DOE direct coal liquefaction process development program. Feed, process, and product samples were used to assess process operations, product quality, and the effects of process variables, and to direct future testing. The primary objective of the Participants Program was to identify and demonstrate analytical methods for use in support of liquefaction process development, and in so doing, provide a bridge between process design, and development, and operation and analytical chemistry. To achieve this objective, novel analytical methods were evaluated for application to direct coal liquefaction-derived materials. CONSOL teamed with 24 research groups in the program. Well-defined and characterized samples of coal liquefaction process-derived materials were provided to each group. CONSOL made an evaluation of each analytical technique. During the performance of this project, we obtained analyses on samples from numerous process development and research programs and we evaluated a variety of analytical techniques for their usefulness in supporting liquefaction process development. Because of the diverse nature of this program, we provide here an annotated bibliography of the technical reports, publications, and formal presentations that resulted from this program to serve as a comprehensive summary of contract activities.

  3. Solvent recyclability in a multistep direct liquefaction process

    SciTech Connect

    Hetland, M.D.; Rindt, J.R.

    1995-12-31

    Direct liquefaction research at the Energy & Environmental Research Center (EERC) has, for a number of years, concentrated on developing a direct liquefaction process specifically for low-rank coals (LRCs) through the use of hydrogen-donating solvents and solvents similar to coal-derived liquids, the water/gas shift reaction, and lower-severity reaction conditions. The underlying assumption of all of the research was that advantage could be taken of the reactivity and specific qualities of LRCs to produce a tetrahydrofuran (THF)-soluble material that might be easier to upgrade than the soluble residuum produced during direct liquefaction of high-rank coals. A multistep approach was taken to produce the THF-soluble material, consisting of (1) preconversion treatment to prepare the coal for solubilization, (2) solubilization of the coal in the solvent, and (3) polishing to complete solubilization of the remaining material. The product of these three steps can then be upgraded during a traditional hydrotreatment step. The results of the EERC`s research indicated that additional studies to develop this process more fully were justified. Two areas were targeted for further research: (1) determination of the recyclability of the solvent used during solubilization and (2) determination of the minimum severity required for hydrotreatment of the liquid product. The current project was funded to investigate these two areas.

  4. Coal liquefaction process streams characterization and evaluation

    SciTech Connect

    Brandes, S.D.; Winschel, R.A.; Burke, F.P.

    1992-11-01

    This is the twelfth Quarterly Technical Progress Report under DOE Contract DE-AC22-89PC89883. Major topics reported are: Summaries of the final reports produced by Lehigh University, West Virginia University, and Vander Sande Associates under the Participants Program are presented. Analytical data produced by CONSOL are provided in Appendix I for all samples employed in the Participants Program and issued with the samples to research groups in the Participants Program. A paper was presented at the 1992 US Department of Energy Pittsburgh Energy Technology Center Liquefaction Contractors' Review Conference, held in Pittsburgh September 23--24, 1992, entitled The Chemical Nature of Coal Liquid Resids and the Implications for Process Development''. It appears as Appendix 2 in this report.

  5. Direct liquefaction proof-of-concept program. Topical report

    SciTech Connect

    Comolli, A.G.; Lee, L.K.; Pradhan, V.R.

    1996-12-01

    This report presents the results of work conducted under the DOE Proof-of-Concept Program in direct coal liquefaction at Hydrocarbon Technologies, Inc. in Lawrenceville, New Jersey, from February 1994 through April 1995. The work includes modifications to HRI`s existing 3 ton per day Process Development Unit (PDU) and completion of the second PDU run (POC Run 2) under the Program. The 45-day POC Run 2 demonstrated scale up of the Catalytic Two-Stage Liquefaction (CTSL Process) for a subbituminous Wyoming Black Thunder Mine coal to produce distillate liquid products at a rate of up to 4 barrels per ton of moisture-ash-free coal. The combined processing of organic hydrocarbon wastes, such as waste plastics and used tire rubber, with coal was also successfully demonstrated during the last nine days of operations of Run POC-02. Prior to the first PDU run (POC-01) in this program, a major effort was made to modify the PDU to improve reliability and to provide the flexibility to operate in several alternative modes. The Kerr McGee Rose-SR{sup SM} unit from Wilsonville, Alabama, was redesigned and installed next to the U.S. Filter installation to allow a comparison of the two solids removal systems. The 45-day CTSL Wyoming Black Thunder Mine coal demonstration run achieved several milestones in the effort to further reduce the cost of liquid fuels from coal. The primary objective of PDU Run POC-02 was to scale-up the CTSL extinction recycle process for subbituminous coal to produce a total distillate product using an in-line fixed-bed hydrotreater. Of major concern was whether calcium-carbon deposits would occur in the system as has happened in other low rank coal conversion processes. An additional objective of major importance was to study the co-liquefaction of plastics with coal and waste tire rubber with coal.

  6. Highly dispersed catalysts for coal liquefaction

    SciTech Connect

    Hirschon, A.S.; Wilson, R.B. Jr.

    1992-06-08

    Iron and molybdenum complexes were studied as precursors to high dispersion catalysts for coal liquefaction. The precursors were either organometallic complexes or water soluble salts and were impregnated into coals of various ranks. The molybdenum catalysts were found to be very effective for conversion of an Illinois {number sign}6 bituminous coal whereas the iron catalysts were not. In contrast, the iron catalysts were found to be very effective for lignite conversions. A H-donor and a non-donor conversion system were compared, using tetralin and n-hexadecane, respectively. In each case the organometallic precursor gave greater yields of toluene soluble material, with differences being most dramatic in the hexadecane system. The yields using the organometallic molybdenum precursors in hexadecane were found to be almost as great as those in the tetralin system, indicating that good catalyst precursors do not require donor solvents. The impregnation techniques were evaluated by comparing conversion yields and analyzing the products using Field Ionization Mass Spectroscopy (f.i.m.s) and FT-IR.

  7. Coal liquefaction. Quarterly report, July-September 1979

    SciTech Connect

    1980-07-01

    The status of coal liquefaction pilot plants supported by US DOE is reviewed under the following headings: company involved, location, contract, funding, process name, process description, flowsheet, history and progress during the July-September 1979 quarter. Supporting projects such as test facilities, refining and upgrading coal liquids, catalyst development, and gasification of residues from coal gasification plants are discussed similarly. (LTN)

  8. Coal liquefaction process streams characterization and evaluation: FT-IR methods for characterization of coal liquefaction products

    SciTech Connect

    Serio, M.A.; Teng, H.; Bassilakis, R.; Solomon, P.R.

    1992-04-01

    This study was designed to demonstrate the use of two FTIR techniques for the analysis of direct coal liquefaction process-derived materials. The two methods were quantitative FTIR analysis and themogravimetric (TG) analysis with FTIR analysis of evolved products (TG-FTIR). The quantitative FTIR analyses of both whole resids and THF-soluble resids provided quantitation of total hydrogen, aliphatic and aromatic hydrogen, total carbon, total oxygen, hydroxyl and etheric oxygen, and ash contents. The FTIR results were usually in agreement with values derived by other, more conventional methods. However, the accuracies of specific measurements, in comparisons with results from conventional methods, ranged from good to poor. The TG-FTIR method provided approximate analyses of coals and resids. The data provided included the time dependent evolution profiles of the volatile species and the elemental composition of the char. Reproducible data of gaseous species and pyrolysis tar yields for whole resid samples larger than 10 mg were obtainable. The yields and evolution profiles of certain volatiles (tar, CO, and methane) provided structural information on the samples. There were some experimental and interpretational difficulties associated with both techniques. Optimization of the curve-resolving routine for coal-liquefaction samples would improve the quantitative FTIR accuracy. Aerosol formation limited the full application of the TG-FTIR technique with the THF-soluble resid samples. At this time, further development of these analytical methods as process development tools will be required before their use for that purpose can be recommended. The use of FTIR as an on-line analytical technique for coal liquefaction process streams requires demonstration before it can be recommended; however, such a demonstration may be warranted.

  9. Microbial recovery of metals from spent coal liquefaction catalysts. Quarterly report, January 1994--March 1994

    SciTech Connect

    Sandbeck, K.A.; Cleveland, D.H.

    1994-07-01

    Mo release from spent coal liquefaction catalysts has been shown to be dependent upon many parameters, but release is dominated by microbial growth. The microbial Mo release is a rapid process requiring less than one week for 90% of the releaseable Mo to be solubilized from whole washed (THF) catalyst. It could be expected that the rates would be even greater with crushed catalyst. Efforts are now centering on optimizing the parameters that stimulate microbial growth and action.

  10. Coal liquefaction process streams characterization and evaluation: Electron microscopy observations of resids obtained from coal liquefaction experiments

    SciTech Connect

    Vander Sande, J.B.

    1992-11-01

    The study demonstrated the feasibility of using scanning transmission electron microscopy (STEM) spectroscopy accompanied by energy dispersive X-ray (EDX) spectroscopy for the examination of the (THF)-insoluble portion of distillation resid materials derived from direct coal liquefaction. The technique was able to determine the distribution, morphology and elemental composition of dispersed catalyst components in the insoluble portion of the distillation resids. An attempt was made to use transmission electron microscopy (TEM) on these samples; however, detailed compositional information could not be obtained. Further development of STEM and EDX as aids to process development are justified based on these results.

  11. Coal liquefaction process streams characterization and evaluation: [sup 13]C-NMR analysis of CONSOL THF-soluble residual materials from the Wilsonville coal liquefaction process

    SciTech Connect

    Solum, M.S.; Pugmire, R.J. )

    1992-11-01

    This study demonstrated the feasibility of using CP/MAS [sup 13]C-NMR spectroscopy for the chemical structural examination of distillation resid materials derived from direct coal liquefaction. A set of twelve carbon skeletal-structure parameters and eight molecular structural descriptors were derived from the NMR data. The technique was used previously to determine these parameters for coal and char, and in the construction of a coal pyrolysis model. The method was applied successfully to the tetrahydrofuran (THF)-soluble portion of eleven 850[degrees]F[sup +] distillation resids and one 850[degrees]F[sup +] distillation resid which contained ash and insoluble organic material (IOM). The results of this study demonstrate that this analytical method can provide data for construction of a model of direct coal liquefaction. Its further development and use is justified based on these results.

  12. Coal liquefaction process streams characterization and evaluation: {sup 13}C-NMR analysis of CONSOL THF-soluble residual materials from the Wilsonville coal liquefaction process

    SciTech Connect

    Solum, M.S.; Pugmire, R.J.

    1992-11-01

    This study demonstrated the feasibility of using CP/MAS {sup 13}C-NMR spectroscopy for the chemical structural examination of distillation resid materials derived from direct coal liquefaction. A set of twelve carbon skeletal-structure parameters and eight molecular structural descriptors were derived from the NMR data. The technique was used previously to determine these parameters for coal and char, and in the construction of a coal pyrolysis model. The method was applied successfully to the tetrahydrofuran (THF)-soluble portion of eleven 850{degrees}F{sup +} distillation resids and one 850{degrees}F{sup +} distillation resid which contained ash and insoluble organic material (IOM). The results of this study demonstrate that this analytical method can provide data for construction of a model of direct coal liquefaction. Its further development and use is justified based on these results.

  13. Changes in organic sulfur compounds in coal macerals during liquefaction

    SciTech Connect

    Winans, R.E.; Joseph, J.T.; Fisher, R.B.

    1994-12-31

    Environmentally sound use of coal for energy production involves effective sulfur removal from the feed coal and/or coal-derived products. Physical cleaning of coal is effective in removing substantial quantities of inorganic sulfur compounds such a pyrite. However, removal of organic sulfur by physical means has not been extremely successful. It is likely that only chemical methods will be useful in substantial removal of organic sulfur. A thorough knowledge of the chemistry of organic sulfur in coal will be valuable in attempts to remove organic sulfur from coal or its liquefaction or pyrolysis products by chemical methods. Since different coal macerals have different liquefaction reactivities, the analysis of sulfur functionalities on separated macerals is deemed to be more meaningful than studying the whole coal. Liquefaction behavior and organic sulfur speciation of the macerals separated from Lewiston-Stockton coal (Argonne Premium Coal Sample bank, APCS-7) by XPS, XANES, and HRMS has been previously described. This paper describes the preliminary speciation of sulfur compounds in the asphaltene fraction of the liquefaction products from these macerals.

  14. Coal liquefaction process streams characterization and evaluation

    SciTech Connect

    Brandes, S.D.; Lancet, M.S.; Robbins, G.A.; Winschel, R.A.; Burke, F.P.

    1992-11-01

    This is the eleventh Quarterly Technical Progress Report under DOE Contract DE-AC22-89PC89883. Major topics reported are: (1) The results of a study designed to determine the effects of the conditions employed at the Wilsonville slurry preheater vessel on coal conversion is described. (2) Stable carbon isotope ratios were determined and used to source the carbon of three product samples from Period 49 of UOP bench-scale coprocessing Run 37. The results from this coprocessing run agree with the general trends observed in other coprocessing runs that we have studied. (3) Microautoclave tests and chemical analyses were performed to calibrate'' the reactivity of the standard coal used for determining donor solvent quality of process oils in this contract. (4) Several aspects of Wilsonville Close-Coupled Integrated Two-Stage Liquefaction (CC-ITSL) resid conversion kinetics were investigated; results are presented. Error limits associated with calculations of deactivation rate constants previously reported for Runs 258 and 261 are revised and discussed. A new procedure is described that relates the conversions of 850[degrees]F[sup +] , 1050[degrees]F[sup +], and 850 [times] 1050[degrees]F material. Resid conversions and kinetic constants previously reported for Run 260 were incorrect; corrected data and discussion are found in Appendix I of this report.

  15. Corrosion coupon studies at coal liquefaction pilot plants

    SciTech Connect

    Keiser, J.R.; Baylor, V.B.; Howell, M.; Newsome, J.F.

    1983-09-01

    As part of the Fossil Energy Materials Program at Oak Ridge National Laboratory, we have supplied corrosion coupons to coal-liquefaction pilot plants for exposure in selected vessels. These vessels were chosen on the basis of previous corrosion experience, anticipated corrosion behavior (especially important when operating conditions were changed), accessibility, and availability. Alloys exposed were selected to give a series with a corrosion resistance ranging from less than to greater than that thought to be needed for each application. Corrosion rates calculated from weight changes of the exposed coupons provide information useful in selecting materials for coal-liquefaction plants. The results presented are from coupons exposed in the Wilsonville, Alabama, and Fort Lewis, Washington, Solvent Refined Coal pilot plants; the Catlettsburg, Kentucky, H-Coal Pilot Plant; and the Baytown, Texas, Exxon Coal Liquefaction Pilot Plant.

  16. ENVIRONMENTAL ASSESSMENT DATA BASE FOR COAL LIQUEFACTION TECHNOLOGY: VOLUME I. SYSTEMS FOR 14 LIQUEFACTION PROCESSES

    EPA Science Inventory

    The two-volume report, prepared as part of an overall environmental assessment (EA) program for the technology involved in the conversion of coal to clean liquid fuels, and the Standards of Practice Manual for the Solvent Refined Coal Liquefaction Process (EPA-600/7-78-091) repre...

  17. Advanced concepts in coal liquefaction: Optimization of reactor configuration in coal liquefaction. Final report

    SciTech Connect

    Pradhan, V.R.; Comolli, A.G.; Lee, L.K.

    1994-11-01

    The overall objective of this Project was to find the ways to effectively reduce the cost of coal liquids to about dollar 25 per barrel of crude oil equivalent. The work described herein is primarily concerned with the testing at the laboratory scale of three reactor configuration concepts, namely (1) a fixed-bed plug-flow reactor as a ``finishing reactor`` in coal liquefaction, (2) three-stage well-mixed reactors in series, and (3) interstage stream concentration/product separation. The three reactor configurations listed above were tested during this project using a 20 cc tubing microreactor, a fixed-bed plug flow reactor, and a two-stage modified Robinson-Mahoney reactor system. The reactor schemes were first evaluated based on theoretical modelling studies, then experimentally evaluated at the microautoclave level and laboratory scale continuous operations. The fixed-bed ``finishing reactor`` concept was evaluated in both the upflow and the downflow modes of operation using a partially converted coal-solvent slurry as feed. For most of the testing of concepts at the microautoclave level, simulated coal, recycle oil, and slurry feedstocks were either specially prepared (to represent a specific state of coal/resid conversion) and/or obtained from HRI`s other ongoing bench-scale and PDU scale coal liquefaction experiments. The three-stage continuous stirred tank reactors (CSTR) and interstage product stream separation/concentration concepts were tested using a simulated three-stage CSTR system by employing a laboratory-scale ebullated-bed system and a modified version of the HRI`s existing Robinson-Mahoney fixed catalyst basket reactor system. This testing was conducted as a fourteen day long continuous run, divided into four Conditions to allow for a comparison of the new three-stage CSTR and interstage product concentration concepts with a two-stage CSTR baseline configuration.

  18. Liquefaction of calcium-containing subbituminous coals and coals of lower rank

    DOEpatents

    Gorbaty, Martin L.; Taunton, John W.

    1980-01-01

    A process for the treatment of a calcium-containing subbituminous coal and coals of lower rank to form insoluble, thermally stable calcium salts which remain within the solids portions of the residue on liquefaction of the coal, thereby suppressing the formation scale, made up largely of calcium carbonate deposits, e.g., vaterite, which normally forms within the coal liquefaction reactor (i.e., coal liquefaction zone), e.g., on reactor surfaces, lines, auxiliary equipment and the like. A solution of a compound or salt characterized by the formula MX, where M is a Group IA metal of the Periodic Table of the Elements, and X is an anion which is capable of forming water-insoluble, thermally stable calcium compounds, is maintained in contact with a particulate coal feed sufficient to impregnate said salt or compound into the pores of the coal. On separation of the impregnated particulate coal from the solution, the coal can be liquefied in a coal liquefaction reactor (reaction zone) at coal liquefaction conditions without significant formation of vaterite or other forms of calcium carbonate on reactor surfaces, auxiliary equipment and the like; and the Group IA metal which remains within the liquefaction bottoms catalyzes the reaction when the liquefaction bottoms are subjected to a gasification reaction.

  19. Enhanced coal liquefaction by pyrolysis in supercritical fluids

    SciTech Connect

    Paulaitis, M.E.; Klein, M.T.; Sandler, S.I.

    1990-11-19

    A fundamental investigation of a novel coal liquefaction process was undertaken which combines pyrolysis and supercritical-fluid solvent extraction. The experimental work consisted of determining: (1) coal pyrolysis reaction pathways, kinetics and mechanisms; (2) equilibrium solubilities of coal-related compounds in supercritical water. Experiments involving model coal compounds (tetralin and 1-methylnaphthalene, phenethyl phenyl ether, 1,3-diphenylpropane, benzyl phenyl ether, benzylamine). 8 refs., 6 figs., 9 tabs.

  20. Activity and selectivity of molybdenum catalysts in coal liquefaction reactions

    SciTech Connect

    Curtis, C.W.; Pellegrino, J.L. )

    1988-06-01

    During coal liquefaction, coal fragments forming a liquid product with reduced heteroatom content. Coal can be considered to be a large network of polynuclear aromatic species connected by heteroatoms and alkyl bridging structures. Predominant heteroatoms contained in coal are sulfur, oxygen, and nitrogen. Predominant alkyl bridges are methylene and ethylene structures. The purpose of this work is to evaluate how effectively three different molybdenum catalysts promote reactions involving heteroatom removal and cleavage of alkyl bridge structures. The reactions studied include: hydrogenation (HYD), hydrodeoxygenation (HDO), hydrosulfurization (HDS), hydrodenitrogenation (HDN) and hydrocracking (HYC). Both model and coal liquefaction reactions were performed to test the activity and selectivity of three different molybdenum catalysts. The three catalysts used were molybdenum napththenate, molybdenum supported on gamma alumina (Mo/Al/sub 2/O/sub 3/) and precipitated, poorly crystalline molybdenum disulfide (MoS/sub 2/). The model compounds, chosen to mimic coal structure, on which the effectiveness of the catalysts for the model reactions was tested were: 1-methylnaphthalene, representing aromatic hydrocarbons, for hydrogenation; 1-naphthol, representing oxygen containing compounds, for deoxygenation; benzothiophene, representing sulfur containing compounds, for desulfurization; indole, representing nitrogen containing compounds, for denitrogenation; and bibenzyl, representing alkyl bridging structures, for hydrocracking. Catalytic reactions of combinations of reactants were performed to simulate a complex coal matrix. Thermal and catalytic coal liquefaction reactions were performed using Illinois No. 6 coal with anthracene as a solvent. The efficacy of the catalysts was determined by comparing the product and compound class fractions obtained from the liquefaction reactions.

  1. Geological occurrence response to trace elemental migration in coal liquefaction based on SPSS: take no. 11 coalbed in Antaibao mine for example

    NASA Astrophysics Data System (ADS)

    Xia, Xiaohong; Qin, Yong; Yang, Weifeng

    2013-03-01

    Coal liquefaction is an adoptable method to transfer the solid fossil energy into liquid oil in large scale, but the dirty material in which will migrate to different step of liquefaction. The migration rule of some trace elements is response to the react activity of macerals in coal and the geological occurrence of the element nature of itself. In this paper, from the SPSS data correlation analysis and hierarchical clustering dendrogram about the trace elements with macerals respond to coal liquefaction yield, it shows the trace elements in No.11 Antaibao coal seam originated from some of lithophile and sulphophle elements. Correlation coefficient between liquefaction yield of three organic macerals and migration of the elements in liquefaction residue indicated that the lithophile are easy to transfer to residue, while sulphophle are apt to in the liquid products. The activated macerals are response to sulphophle trace elements. The conclusion is useful to the coal blending and environmental effects on coal direct liquefaction.

  2. Progress in donor assisted coal liquefaction: Hydroaromatic compound formation

    SciTech Connect

    Kottenstette, R.J.; Stephens, H.P.

    1993-12-31

    The role of hydrogen donor compounds in coal liquefaction has been extensively investigated since the mid 1960`s using model compounds and process derived hydrogen donor solvents. Our recent research and that of other investigators have shown that two model compounds in particular have great efficacy in solvating low rank coals. 1,2,3,10b tetrahydrofluoranthene (H{sub 4}Fl) and 1,2,3,6,7,8 hexahydropyrene (H{sub 6}Py) have been used to dissolve Wyodak coal to > 95% soluble material as measured by tetrahydrofuran (THF). Although these hydrogen donors are very effective, they may not be found in any significant concentrations in actual liquefaction process recycle solvents. Therefore, studies with process derived recycle materials are necessary to understand donor solvent chemistry. The objective of this paper is to present results of solvent hydrogenation experiments using heavy distillate solvents produced during testing at the Wilsonville Advanced Coal Liquefaction Test Facility. We evaluated the impact of hydrogenation conditions upon hydrogen donor formation in process derived distillates and compared these process derived solvents with the highly effective H{sub 4}Fl and H{sub 6}Py donors in coal liquefaction tests. This paper presents data on reaction conditions used for distillate hydrotreating and subsequent coal liquefaction, with an aim toward understanding the relationship between reaction conditions and donor solvent quality in recycle distillates.

  3. Exploratory Research on Novel Coal Liquefaction Concept - Task 2: Evaluation of Process Steps.

    SciTech Connect

    Brandes, S.D.; Winschel, R.A.

    1997-05-01

    A novel direct coal liquefaction technology is being investigated in a program being conducted by CONSOL Inc. with the University of Kentucky, Center for Applied Energy Research and LDP Associates under DOE Contract DE-AC22-95PC95050. The novel concept consists of a new approach to coal liquefaction chemistry which avoids some of the inherent limitations of current high-temperature thermal liquefaction processes. The chemistry employed is based on hydride ion donation to solubilize coal at temperatures (350-400{degrees}C) significantly lower than those typically used in conventional coal liquefaction. The process concept being explored consists of two reaction stages. In the first stage, the coal is solubilized by hydride ion donation. In the second, the products are catalytically upgraded to acceptable refinery feedstocks. The program explores not only the initial solubilization step, but integration of the subsequent processing steps, including an interstage solids-separation step, to produce distillate products. A unique feature of the process concept is that many of the individual reaction steps can be decoupled, because little recycle around the liquefaction system is expected. This allows for considerable latitude in the process design. Furthermore, this has allowed for each key element in the process to be explored independently in laboratory work conducted under Task 2 of the program.

  4. New catalysts for coal liquefaction and new nanocrystalline catalysts synthesis methods

    SciTech Connect

    Linehan, J.C.; Matson, D.W.; Darab, J.G.

    1994-09-01

    The use of coal as a source of transportation fuel is currently economically unfavorable due to an abundant world petroleum supply and the relatively high cost of coal liquefaction. Consequently, a reduction in the cost of coal liquefaction, for example by using less and/or less costly catalysts or lower liquefaction temperatures, must be accomplished if coal is to play an significant role as a source of liquid feedstock for the petrochemical industry. The authors and others have investigated the applicability of using inexpensive iron-based catalysts in place of more costly and environmentally hazardous metal catalysts for direct coal liquefaction. Iron-based catalysts can be effective in liquefying coal and in promoting carbon-carbon bond cleavage in model compounds. The authors have been involved in an ongoing effort to develop and optimize iron-based powders for use in coal liquefaction and related petrochemical applications. Research efforts in this area have been directed at three general areas. The authors have explored ways to optimize the effectiveness of catalyst precursor species through use of nanocrystalline materials and/or finely divided powders. In this effort, the authors have developed two new nanophase material production techniques, Modified Reverse Micelle (MRM) and the Rapid Thermal Decomposition of precursors in Solution (RTDS). A second effort has been aimed at optimizing the effectiveness of catalysts by variations in other factors. To this, the authors have investigated the effect that the crystalline phase has on the capacity of iron-based oxide and oxyhydroxide powders to be effectively converted to an active catalyst phase under liquefaction conditions. And finally, the authors have developed methods to produce active catalyst precursor powders in quantities sufficient for pilot-scale testing. Major results in these three areas are summarized.

  5. Fundamental studies of retrograde reactions in direct liquefaction. Topical report, September 30, 1988--September 30, 1989

    SciTech Connect

    Serio, M.A.; Solomon, P.R.; Bassilakis, R.; Kroo, E.

    1989-12-31

    Most of the proposed processing schemes for improving liquefaction yields involve favoring bond-breaking and radical stabilization reactions over the retrograde reactions. The retrograde reactions are often encountered before liquefaction temperatures are reached. The objective of this program is to elucidate and model the retrograde reaction chemistry in direct coal liquefaction through the application of experimental techniques and theoretical models which have been successfully employed at Advanced Fuel Research (AFR) and SRI International (a subcontractor) to understand and predict coal reaction behavior. The study of retrograde reactions is being done using an integrated approach using extensive characterization of the liquefaction chemistry of three kinds of systems: (1) model polymers; (2) coal; and (3) modified coals.

  6. Novel bimetallic dispersed catalysts for temperature-programmed coal liquefaction

    SciTech Connect

    Song, Chunshan; Schobert, H.H.

    1993-02-01

    Development of new catalysts is a promising approach to more efficient coal liquefaction. It has been recognized that catalysts are superior to supported catalysts for primary liquefaction of coals, because the control of initial coal dissolution or depolymerization requires intimate contact between the catalyst and coal. This research is a fundamental and exploratory study on catalytic coal liquefaction, with the emphasis on the development of novel bimetallic dispersed catalysts for temperature-programmed liquefaction. The ultimate goal of the present research is to develop novel catalytic hydroliquefaction process using highly active dispersed catalysts. The primary objective of this research is to develop novel bimetallic dispersed catalysts from organometallic molecular that can be used in low precursors concentrations (< 1 %) but exhibit high activity for efficient hydroliquefaction of coals under temperature-programmed conditions. The major technical approaches are, first, to prepare the desired heteronuclear organometallic molecules as catalyst precursors that contain covalently bound, two different metal atoms and sulfur in a single molecule. Such precursors will generate finely dispersed bimetallic catalysts such as Fe-Mo, Co-Mo and Ni-Mo binary sulfides upon thermal decomposition. The second major technical approach is to perform the liquefaction of coals unpregnated with the organometallic precursors under temperature-programmed conditions, where the programmed heat-up serves as a step for both catalyst activation and coal pretreatment or preconversion. Two to three different complexes for each of the Fe-Mo, Co-Mo, and Ni-Mo combinations will be prepared. Initial catalyst screening tests will be conducted using a subbituminous coal and a bituminous coal. Effects of coal rank and solvents will be examined with the selected bimetallic catalysts which showed much higher activity than the dispersed catalysts from conventional precursors.

  7. Coal liquefaction process streams characterization and evaluation. Volume 2, Participants program final summary evaluation

    SciTech Connect

    Brandes, S.D.; Robbins, G.A.; Winschel, R.A.; Burke, F.P.

    1994-05-01

    This 4.5-year project consisted of routine analytical support to DOE`s direct liquefaction process development effort (the Base Program), and an extensive effort to develop, demonstate, and apply new analytical methods for the characterization of liquefaction process streams (the Participants Program). The objective of the Base Program was to support the on-going DOE direct coal liquefaction process development program. Feed, process, and product samples were used to assess process operations, product quality, and the effects of process variables, and to direct future testing. The primary objective of the Participants Program was to identify and demonstrate analytical methods for use in support of liquefaction process develpment, and in so doing, provide a bridge between process design, development, and operation and analytical chemistry. To achieve this direct coal liquefaction-derived materials. CONSOL made an evaluation of each analytical technique. During the performance of this project, we obtained analyses on samples from numerous process development and research programs and we evaluated a variety of analytical techniques for their usefulness in supporting liquefaction process development. Because of the diverse nature of this program, we provide here an annotated bibliography of the technical reports, publications, and formal presentations that resulted from this program to serve as a comprehensive summary of contract activities.

  8. Characteristics and Thermal Behaviour of Low Rank Malaysian Coals towards Liquefaction Performance via Thermogravimetric Analysis

    NASA Astrophysics Data System (ADS)

    Ishak, M. A. M.; Ismail, K.; Nawawi, W. I.; Jawad, A. H.; Abdullah, M. F.; Kasim, M. N.; Ani, A. Y.

    2016-07-01

    In this study, thermal behaviour of two low-rank Malaysian coals namely Mukah Balingian (MB) and Batu Arang (BA) were obtained under pyrolysis conditions via Thermogravimetric analysis (TGA) at a heating rate of 20°C min-1. The thermal characteristics of the coals were investigated prior to direct liquefaction in order to determine the liquefaction performance, i.e. coal conversion and oil yield. The differential weight loss (DTG) results for both coals showed that there are three main stages evolved which consists of moisture, volatile matter and heavier hydrocarbons that correspond to temperature range of 150, 200-500 and 550-800°C, respectively. Apparently, the DTG curves of BA coal reveals a similar pattern of thermal evolution profile in comparison to that of the MB coal. However, the calculated mean reactivity of BA coal is higher than that of MB, which implied that BA would probably enhance coal conversion and oil yield in comparison to MB coal. Interestingly, results showed that under the same liquefaction conditions (i.e. at 4MPa pressure and 420°C), conversion and oil yield of both coals were well correlated with their reactivity and petrofactor value obtained.

  9. Environmental studies of materials from the H-coal liquefaction process development unit

    SciTech Connect

    Cada, G.F.

    1982-12-01

    H-coal is a process for the direct liquefaction of coal to produce synthetic fuels. Its development has progressed from bench-scale testing through operation of a 2.7 Mg/d (3 ton/d) Process Development Unit. A large-scale H-Coal pilot plant is presently operating at Catlettsburg, Kentucky, and there are plans for the construction of a commercial H-Coal liquefaction facility by the end of the decade. Two of the environmental concerns of the developing direct coal liquefaction industry are accidental spills of synthetic oils and treatment/storage of solid wastes. As a means of obtaining preliminary information on the severity of these potential impacts well in advance of commercialization, samples of product oils and solid wastes were obtained from the H-Coal Process Development Unit (PDU). These samples were subjected to a battery of rapid screening tests, including chemical characterization and bioassays with a variety of aquatic and terrestrial organisms. Water-soluble fraction (WSFs) of H-Coal PDU oils had considerably higher concentrations of phenols and anilines and were commonly one to two orders of magnitude more toxic to aquatic organisms than WSFs of analogous petroleum crude oil. Whole H-Coal PDU oils were also more toxic to the cricket than petroleum-based oils, and some H-Coal samples showed evidence of teratogenicity. Leachates from H-Coal PDU solid wastes, on the other hand, had relatively low concentrations of selected elements and had essentially no acute toxicity to a variety of aquatic and terrestrial species. These studies indicate that environmental effects of product oil spills from a commercial H-Coal liquefaction plant are likely to be more severe than those of conventional petroleum spills. Product upgrading or special transportation and storage techniques may be needed to ensure environmentally sound commercialization of the H-Coal process.

  10. Exploratory research on novel coal liquefaction concept. [Quarterly report], May 24--September 30, 1995

    SciTech Connect

    Burke, F.P.; Winschel, R.A.; Brandes, S.D.; Derbyshire, F.J.; Kimber, G.; Anderson, R.K.; Carter, S.D.; Peluso, M.

    1995-11-08

    CONSOL Inc., the University of Kentucky/Center for Applied Energy Research (CAER), and LDP Associates are conducting a three-year research program to explore the technical and economic feasibility of a novel direct coal liquefaction concept. The purpose of this research program is to explore a new approach to direct coal liquefaction in which the primary coal dissolution step is effected by chemical rather than thermal cleavage of bonds in the coal. This is done at a temperature which is significantly lower than that typically used in conventional coal liquefaction. Reaction at this low temperature results in high conversion of the coal to a solubilized form, with little hydrocarbon gas make, and avoids the thermally induced retrograde reactions which are unavoidable in conventional thermal processes. In addition, for low-rank coals, a substantial portion of the oxygen in the coal is removed as CO and CO{sub 2} during the dissolution. The higher selectivity to liquid products and rejection of oxygen as carbon oxides should result in improved hydrogen utilization. The basis of the novel concept is the discovery made by CONSOL R&D that certain hydride transfer agents are very active for coal dissolution at temperatures in the range of 350{degree}C. Because of the exploratory nature of the research, the project is divided into sequential tasks that are designed to first evaluate key elements of the process is presented for the following tasks: management plan; evaluation of process steps; engineering and economic study and reporting.

  11. Advanced liquefaction using coal swelling and catalyst dispersion techniques. Quarterly progress report, July--September 1993

    SciTech Connect

    Curtis, C.W.; Gutterman, C.; Chander, S.

    1993-12-31

    The overall objective of this project is 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 integrates coal selection, pretreatment, coal swelling with catalyst impregnation, liquefaction, product recovery with characterization, alternate bottoms processing, and carrying out a technical assessment including an economic evaluation. The primary coal of this program, Black Thunder subbituminous coal, can be effectively beneficiated to about 3.5 wt % ash using aqueous sulfurous acid pretreatment. This treated coal can be further beneficiated to about 2 wt % ash using commercially available procedures. All three coals used in this study (Black Thunder, Burning Star bituminous, and Martin Lake lignite) are effectively swelled by a number of solvents. The most effective solvents are those having hetero-functionality. laboratory- and bench-scale liquefaction experimentation is underway using swelled and catalyst impregnated coal samples. Higher coal conversions were observed for the SO{sub 2}-treated subbituminous coal than the raw coal, regardless of catalyst type. Conversions of swelled coal were highest when Molyvan L, molybdenum naphthenate, and nickel octoate, respectively, were added to the liquefaction solvent. The study of bottoms processing consists of combining the ASCOT process which consists of coupling solvent deasphalting with delayed coking to maximize the production of coal-derived liquids while rejecting solids within the coke drum. The asphalt production phase has been completed; representative product has been evaluated. The solvent system for the deasphalting process has been established. Two ASCOT tests produced overall liquid yields (63.3 wt % and 61.5 wt %) that exceeded the combined liquid yields from the vacuum tower and ROSE process.

  12. Surface Modified Coals for Enhanced Catalyst Dispersion and Liquefaction

    SciTech Connect

    Yaw D. Yeboah

    1998-12-04

    The aim of this study is to enhance catalyst loading and dispersion in coal for improved liquefaction by preadsorption of surfactants and catalysts on to the coal. During this reporting period, liquefaction experiments were conducted with the raw coal and catalyst loaded samples. Pretreatment of the coal and catalyst-loaded samples were done using the surfactants presented in previous reports. Liquefaction samples were tested using 6.6 g of solvent, 3.3 g coal, 6.9 MPa ambient hydrogen pressure, 425 0 C and 30 minutes. The liquid and solid products were removed from the reactor using tetrahydrofuran (THF). Coal conversions were calculated based on THF and heptane solubility. The results showed that in the absence of a catalyst, 33.8% heptane solubles was obtained with the parent coal compared to 27.8% and 27.3% with the SDS and DDAB surfactants. The presence of molybdenum, as expected, resulted in enhanced heptane solubles with or without surfactants. In the absence of surfactants, 50% heptane solubles was obtained compared to 40-47% with surfactants. Thus, it appears that pretreatment, unexpectedly, had a negative effect on liquefaction activity. It is unclear if the observed differences in results are significant. Clearly, additional experiments are needed before any firm deductions and conclusions can be drawn from the results.

  13. Solvent treatment of coal for improved liquefaction

    DOEpatents

    Appell, Herbert R.; Narain, Nand K.; Utz, Bruce R.

    1986-05-06

    Increased liquefaction yield is obtained by pretreating a slurry of solid carbonaceous material and a liquid hydrocarbonaceous solvent at a temperature above 200.degree. C. but below 350.degree. C. for a period of 10 minutes to four hours prior to exposure to liquefaction temperatures.

  14. Microbial recovery of metals from spent coal liquefaction catalysts. Quarterly report, October 1993--December 1993

    SciTech Connect

    Sandbeck, K.A.; Joffe, P.M.

    1993-12-31

    The project objectives outlined in the previous reports involved defining conditions and cultures best suited to achieve the most effective metal release from spent coal liquefaction catalysts by microbial processes. The continuity of the research program was maintained during the period of principal investigator replacement. This transition period allowed the project data to be reviewed and research plans were formulated to gain new insights into the mechanisms involved in metals release. Various microbiological and physiochemical parameters which may be important in microbial release of metals from spent coal liquefaction catalysts continue to be investigated so that this technology can be optimized. Mo release from spent coal liquefaction catalysts has been shown to be dependent upon many parameters, but release is dominated by microbial growth. The microbial Mo release is a rapid process requiring less than one week for 90% of the releasable Mo to be solubilized from whole washed (THF) catalyst. It could be expected that the rates would be even greater with crushed catalyst. Efforts are now centering on optimizing the parameters that stimulate microbial growth and action.

  15. Reducing viscosity of coal-liquefaction products with additives

    SciTech Connect

    Chao, T.S.; Kutta H.W.; Smith, A.C. Jr.

    1980-01-01

    A research program to investigate the cause of high viscosity of coal liquefaction products and to improve this critical property was carried out at Harvey Technical Center under the joint sponsorship by Electric Power Research Institute and Atlantic Richfield Company. Prior to this joint program an in-house project was also initiated by Atlantic Richfield to determine causes and remedies for high viscosity of coal liquefaction products. One result of these programs is the discovery that certain chemical compounds, when used at concentrations of 1 to 10%, are effective in reducing the melt viscosity and softening temperature of these coal liquefaction products. These compounds can be divided into two groups, reactive and unreactive additives. Acids, anhydrides, amides and epoxides fall in the reactive group, while pyrrolidines and compounds belonging to the chemical classes of amides, phosphoramides, lactams and ketones belong to the unreactive additives. This paper summarizes findings on this subject and explains the mechanism of action involved.

  16. Short Contact Time Direct Coal Liquefactionn Using a Novel Batch Reactor. Quarterly Report. May 16 - August 15, 1996

    SciTech Connect

    He Huang; Michael T. Klein; William H. Calkins

    1996-08-30

    The objective of this research is to optimize the design and operation of the bench scale batch reactor (SCTBR) for studying direct coal liquefaction at short contact times (.01 to 10 minutes or longer). Additional objectives are to study the kinetics of direct coal liquefaction particularly at short reaction times and to investigate the role of organic oxygen components of coal and their reaction pathways during coal liquefaction. Many of those objectives have already been achieved. This quarterly report discusses further kinetic studies of the liquefaction of Illinois #6 bituminous coal, Wyodak-Anderson subbituminous coal, and Pittsburgh #8 bituminous coal. The thermodynamic characteristics of the extraction stage at the start of the liquefaction process in the liquefaction of Illinois #6 coal is also discussed. Further work has also been done to attempt to clarify the role of the liquefaction solvent in the direct liquefaction process.

  17. Fine particle clay catalysts for coal liquefaction. Quarterly technical report, May 9, 1991--August 8, 1991

    SciTech Connect

    Olson, E.S.

    1991-12-31

    The efficient production of environmentally acceptable distillate fuels requires catalysts for hydrogenation and cleavage of the coal macromolecules and removal of oxygen, nitrogen, and sulfur heteroatoms. The goal of the proposed research is to develop new catalysts for the direct liquefaction of coal. This type of catalyst consists of fine clay particles that have been treated with reagents which form pillaring structures between the aluminosilicate layers of the clay. The pillars not only hold the layers apart but also constitute the active catalytic sites for hydrogenation of the coal and the solvent used in the liquefaction. The pillaring catalytic sites are composed of pyrrhotite, which has been previously demonstrated to be active for coal liquefaction. The pyrrhotite sites are generated in situ by sulfiding the corresponding oxyiron species. The size of the catalyst will be less than 40 nm in order to promote intimate contact with the coal material. Since the clays and reagents for pillaring and activating the clays are inexpensive, the catalysts can be discarded after use, rather than regenerated by a costly process. The proposed work will evaluate methods for preparing the fine particle iron-pillared clay dispersions and for activating the particles to generate the catalysts. Characterization studies of the pillared clays and activated catalysts will be performed. The effectiveness of the pillared clay dispersion for hydrogenation and coal liquefaction will be determined in several types of testing.

  18. Evaluation of the donor ability of coal liquefaction solvents

    SciTech Connect

    Bockrath, B.C.; Noceti, R.P.

    1981-03-29

    A test was devised to evaluate the donor ability of coal liquefaction solvents. This test embodies the main features of the free radical mechanism of coal liquefaction. Benzyl radicals generated by the thermolysis of a convenient precursor at relatively low temperatures behave like the free radicals generated by the thermolysis of coal at liquefaction temperatures. As precursors for this test, dibenzyldiazene and dibenzylmercury were selected. When benzyl radicals are generated in a donor solvent, the relative amounts of toluene and bibenzyl produced reflect the relative ability of the solvent to donate hydrogen and to prevent recombination. A variable amount of benzyl radical is also lost, which presumably represents that amount which adds to or combines with the solvent. Experimental evidences have shown that an additional mode of action of donor solvent is that of free radical scavenger by combination and addition reactions. Accordingly, three indices were devised to compare donor solvents: the donor, the scavenger, and combined index. The three solvent indices were determined for the decomposition of dibenzylmercury for several solvent mixtures made from different amounts of tetralin (solvent) in t-butyl benzene. The data show that the donor index increases with increasing tetralin concentration. A series of model compounds were evaluated using dibenzyldiazene as the source of benzyl radical, and results are tabulated. Another table is presented which show the donor indices obtained for several coal-derived liquefaction solvents. Taken together, these data indicate that there is good qualitative agreement between liquefaction performance and the donor index of solvents.

  19. SURFACE-MODIFIED COALS FOR ENHANCED CATALYST DISPERSION AND LIQUEFACTION

    SciTech Connect

    Dr. Yaw D. Yeboah

    1999-09-01

    This is the final report of the Department of Energy Sponsored project DE-FGF22-95PC95229 entitled, surface modified coals for enhanced catalyst dispersion and liquefaction. The aims of the study were to enhance catalyst loading and dispersion in coal for improved liquefaction by preadsorption of surfactants and catalysts on the coal and to train and educate minority scientists in catalysts and separation science. Illinois No. 6 Coal (DEC-24) was selected for the study. The surfactants investigated included dodecyl dimethyl ethyl ammonium bromide (DDAB), a cationic surfactant, sodium dodecyl sulfate, an anionic surfactant, and Triton x-100, a neutral surfactant. Ammonium molybdate tetrahydrate was used as the molybdenum catalyst precursor. Zeta potential, BET, FTIR, AFM, UV-Vis and luminescence intensity measurements were undertaken to assess the surface properties and the liquefaction activities of the coal. The parent coal had a net negative surface charge over the pH range 2-12. However, in the presence of DDAB the negativity of the surface charge decreased. At higher concentrations of DDAB, a positive surface charge resulted. In contrast to the effect of DDAB, the zeta potential of the coal became more negative than the parent coal in the presence of SDS. Adsorption of Triton reduced the net negative charge density of the coal samples. The measured surface area of the coal surface was about 30 m{sup 2}/g compared to 77m{sup 2}/g after being washed with deionized water. Addition of the surfactants decreased the surface area of the samples. Adsorption of the molybdenum catalyst increased the surface area of the coal sample. The adsorption of molybdenum on the coal was significantly promoted by preadsorption of DDAB and SDS. Molybdenum adsorption showed that, over a wide range of concentrations and pH values, the DDAB treated coal adsorbed a higher amount of molybdenum than the samples treated with SDS. The infrared spectroscopy (FTIR) and the atomic force

  20. Low-rank coal research: Volume 1, Control technology, liquefaction, and gasification: Final report

    SciTech Connect

    Weber, G.F.; Collings, M.E.; Schelkoph, G.L.; Steadman, E.N.; Moretti, C.J.; Henke, K.R.; Rindt, J.R.; Hetland, M.D.; Knudson, C.L.; Willson, W.G.

    1987-04-01

    Volume I contains articles on SO/sub x//NO/sub x/ control, waste management, low-rank direct liquefaction, hydrogen production from low-rank coals, and advanced wastewater treatment. These articles have been entered individually into EDB and ERA. (LTN)

  1. Coal liquefaction: A research and development needs assessment: Final report, Volume II

    SciTech Connect

    Schindler, H.D.; Burke, F.P.; Chao, K.C.; Davis, B.H.; Gorbaty, M.L.; Klier, K.; Kruse, C.W.; Larsen, J.W.; Lumpkin, R.E.; McIlwain, M.E.; Wender, I.; Stewart, N.

    1989-03-01

    Volume II of this report on an assessment of research needs for coal liquefaction contains reviews of the five liquefaction technologies---direct, indirect, pyrolysis, coprocessing, and bioconversion. These reviews are not meant to be encyclopedic; several outstanding reviews of liquefaction have appeared in recent years and the reader is referred to these whenever applicable. Instead, these chapters contain reviews of selected topics that serve to support the panel's recommendations or to illustrate recent accomplishments, work in progress, or areas of major research interest. At the beginning of each of these chapters is a brief introduction and a summary of the most important research recommendations brought out during the panel discussions and supported by the material presented in the review. A review of liquefaction developments outside the US is included. 594 refs., 100 figs., 60 tabs.

  2. Health effects research in direct coal liquefaction. Studies of H-coal distillates: Phase I. PDU samples - the effects of hydrotreatment

    SciTech Connect

    Epler, J.L.; Fry, R.J.M.; Larimer, F.W.

    1981-11-01

    A multi-divisional effort aimed at the integrated assessment of the health and environmental effects of various coal conversion and shale oil technologies is being carried out. The feasibility of using health effects bioassays to predict the potential biohazard of various H-Coal derived test materials is examined in a coupled chemical and biological approach. The primary focus of the research is the use of preliminary chemical characterizations and preparation for bioassay, followed by testing in short-term assays in order to rapidly ascertain the potential biohazard. Mammalian toxicological assays parallel the testing. Raw and hydrotreated product liquids from process development units of H-Coal and the pilot plant solvent refined coal process were examined for acute toxicity monitored as population growth impairment of Tetrahymena exposed to aqueous extracts and for mutagenic activity monitored as revertants of Salmonella exposed to metabolically activated chemical class fractions. Medium to high severity hydrotreatment appears to be an effective means of reducing biological activity, presumably by reducing the aromaticity and heteroatom content. Five basic mammalian, acute toxicity tests have been conducted with selected H-coal samples and shale oil derivatives. The data show that H-Coal samples are moderately toxic whereas the toxicity of shale oil derived products is slight and comparable to samples obtained from naturally occurring petroleums. No overt skin or eye toxicity was found. The present data reveal that coal-derived distillates generated by the H-coal process are highly carcinogenic to mouse skin. An extreme form of neurotoxicity associated with dermal exposure to one of the lighter, minimally carcinogenic, materials was noted. (DMC)

  3. Controlled short residence time coal liquefaction process

    DOEpatents

    Anderson, Raymond P.; Schmalzer, David K.; Wright, Charles H.

    1982-05-04

    Normally solid dissolved coal product and a distillate liquid product are produced by continuously passing a feed slurry comprising raw feed coal and a recycle solvent oil and/or slurry together with hydrogen to a preheating-reaction zone (26, alone, or 26 together with 42), the hydrogen pressure in the preheating-reaction zone being at least 1500 psig (105 kg/cm.sup.2), reacting the slurry in the preheating-reaction zone (26, or 26 with 42) at a temperature in the range of between about 455.degree. and about 500.degree. C. to dissolve the coal to form normally liquid coal and normally solid dissolved coal. A total slurry residence time is maintained in the reaction zone ranging from a finite value from about 0 to about 0.2 hour, and reaction effluent is continuously and directly contacted with a quenching fluid (40, 68) to substantially immediately reduce the temperature of the reaction effluent to below 425.degree. C. to substantially inhibit polymerization so that the yield of insoluble organic matter comprises less than 9 weight percent of said feed coal on a moisture-free basis. The reaction is performed under conditions of temperature, hydrogen pressure and residence time such that the quantity of distillate liquid boiling within the range C.sub.5 -455.degree. C. is an amount at least equal to that obtainable by performing the process under the same conditions except for a longer total slurry residence time, e.g., 0.3 hour. Solvent boiling range liquid is separated from the reaction effluent and recycled as process solvent.

  4. Cooperative research in coal liquefaction. Technical progress report, May 1, 1993--April 30, 1994

    SciTech Connect

    Huffman, G.P.

    1994-10-01

    Accomplishments for the past year are presented for the following tasks: coliquefaction of coal with waste materials; catalysts for coal liquefaction to clean transportation fuels; fundamental research in coal liquefaction; and in situ analytical techniques for coal liquefaction and coal liquefaction catalysts some of the highlights are: very promising results have been obtained from the liquefaction of plastics, rubber tires, paper and other wastes, and the coliquefaction of wastes with coal; a number of water soluble coal liquefaction catalysts, iron, cobalt, nickel and molybdenum, have been comparatively tested; mossbauer spectroscopy, XAFS spectroscopy, TEM and XPS have been used to characterize a variety of catalysts and other samples from numerous consortium and DOE liquefaction projects and in situ ESR measurements of the free radical density have been conducted at temperatures from 100 to 600{degrees}C and H{sub 2} pressures up to 600 psi.

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

    SciTech Connect

    Robbins, G.A.; Brandes, S.D.; Winschel, R.A.; Burke, F.P.

    1996-07-01

    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.

  6. A characterization and evaluation of coal liquefaction process streams. Quarterly technical progress report, April 1--June 30, 1995

    SciTech Connect

    Robbins, G.A.; Brandes, S.D.; Winschel, R.A.; Burke, F.P.

    1995-09-01

    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. The paper describes activities carried out this quarter. 11 refs., 21 figs., 17 tabs.

  7. A characterization and evaluation of coal liquefaction process streams. Quarterly technical progress report, January 1, through March 31, 1995

    SciTech Connect

    1995-05-01

    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. Accomplishments for this quarter are described.

  8. EDS coal liquefaction process development. Phase V. Monthly technical progress report, June 1-June 30, 1980

    SciTech Connect

    Epperly, W.R.

    1980-07-01

    High pressure bottoms recycle operations were conducted on the 50 pounds/day Recycle Coal Liquefaction Unit (RCLU) with Texas lignite from the Big Brown mine. Results indicate that significant conversion, yield and unit operability advantages can be obtained with Big Brown lignite by operating in the bottoms recycle mode, as compared to coal only operation. Yield data obtained from the one ton-per-day Coal Liquefaction Pilot Plant (CLPP) showed that the C/sub 4/-1000/sup 0/F distillate yield was approximately 44% based on dry, ash-free coal compared to 47% for Wyoming subbituminous coal. No unusual coal-specific problems were noted. Preliminary results from liquefaction of neat bottoms on the Once Through Coal Liquefaction Unit (OTCLU) showed significantly higher (C/sub 4/-1000/sup 0/F) liquid make and 1000/sup 0/F/sup +/ conversion for single pass CLPP bottoms when compared with equilibrium CLPP recycle bottoms. Work began on an engineering screening study to determine the impact of high pressure bottoms recycle on the relative economics of various bottoms processing options. A screening study was undertaken to evaluate various methods of calculating the Required Initial Selling Price (RISP) of coal liquids. Heat and material balances were completed to simulate high pressure vacuum bottoms recycle operations at ECLP within the fuel gas treating and DEA regeneration areas of the plant. A research guidance study was initiated to select preferred bottoms recycle operating conditions for subsequent CLPP operations with Wyoming (Wyodak mine) coal. Fluid bed combustion of vacuum bottoms to supply high-level process heat provides incentives comparable to hybrid boilers, another direct combustion option. Research and development on coal slurry fired heaters, conducted by outside organizations, is currently being reviewed.

  9. Advanced liquefaction using coal swelling and catalyst dispersion techniques. Quarterly technical progress report No. 7, April 1993--June 1993

    SciTech Connect

    Curtis, C.W.; Chander, S.; Gutterman, C.

    1994-09-01

    The overall objective of this project is 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 integrates coal selection, pretreatment, coal swelling with catalyst impregnation, liquefaction, product recovery with characterization, alternate bottoms processing, and carrying out a technical assessment including an economic evaluation. The project is being carried out under contract to the United States Department of Energy. All three coals used in this study (Black Thunder, Burning Star bituminous, and Martin Lake lignite) are effectively swelled by a number of solvents. The most effective solvents are those having hetero-functionality. In addition, a synergistic effect has been demonstrated, in which solvent blends are more effective for coal swelling than the pure solvents alone. Therefore, it will be necessary to use only low levels of swelling agents and yet promote the impregnation of catalyst precursors. The rate of the impregnation of catalyst precursors into swollen coal increases greatly as the effectiveness of the solvent to swell the coal increases. This effect is also demonstrated by improved catalyst precursor impregnation with increased contact temperature. Laboratory- and bench-scale liquefaction experimentation is underway using swelled and catalyst impregnated coal samples. Higher coal conversions were observed for the SO{sub 2}-treated coal than the raw coal, regardless of catalyst type. Conversions of swelled coal were highest when Molyvan-L, molybdenum naphthenate, and nickel octoate, respectively, were added to the liquefaction solvent.

  10. Mild coal pretreatment to improve liquefaction reactivity. Final technical report, September 1990--February 1994

    SciTech Connect

    Miller, R.L.; Shams, K.G.

    1994-07-01

    Recent research efforts in direct coal liquefaction are focused on lowering the level of reaction severity, identification and determination of the causes of retrogressive reactions, and improving the economics of the process. Ambient pretreatment of coals using methanol and a trace amount of hydrochloric acid was extensively studied in connection with low severity coal liquefaction. Ambient pretreatment of eight Argonne coals using methanol/HCl improved THF-soluble conversions 24.5 wt % (maf basis) for Wyodak subbituminous coal and 28.4 wt % for Beulah-Zap lignite with an average increase of 14.9 wt % for the eight Argonne coals at 623 K (350{degrees}C) reaction temperature and 30 minutes reaction time. Optimal pretreatment conditions were determined using Wyodak and Illinois No. 6 coals. Acid concentration was the most important pretreatment variable studied; liquefaction reactivity increased with increasing acid concentration up to 2 vol %. The FTIR spectra of treated and untreated Wyodak coal samples demonstrated formation of carboxylic functional groups during pretreatment, a result of divalent (Ca, Mg) cationic bridge destruction. The extent of liquefaction reactivity directly correlated with the amount of calcium removed during pretreatment, and results from calcium ``addback`` experiments supported the observation that calcium adversely affected coal reactivity at low severity reaction conditions. Model compound studies using benzyl phenyl ether demonstrated that calcium cations catalyzed retrogressive reactions, inhibited hydrogenation reactions at low severity reaction conditions, and were more active at higher reaction temperatures. Based on kinetic data, mechanisms for hydrogenation-based inhibition and base-catalyzed retrogressive reactions are proposed. The base-catalyzed retrogressive reactions are shown to occur via a hydrogen abstraction mechanism where hydrogenation inhibition reactions are shown to take place via a surface quenching mechanism.

  11. Toxicity of a coal liquefaction product to aquatic organisms

    SciTech Connect

    Giddings, J.M.; Parkhurst, B.R.; Gehrs, C.W.; Millemann, R.E.

    1980-07-01

    Using acute bioassay tests a representative coal liquefaction product was compared with a petroleum derived residual fuel oil and a diesel fuel. The acute toxicity of water soluble fractions of the oils to two freshwater algae and one freshwater crustacean was determined.

  12. Catalytic multi-stage liquefaction of coal. Ninth quarterly report, October 1, 1994--December 31, 1994

    SciTech Connect

    Comolli, A.G.; Johnson, E.S.; Lee, L.K.

    1995-06-01

    This quarterly report covers the activities of Catalytic Multi-Stage Liquefaction of Coal during the Period October 1 - December 31, 1994, at Hydrocarbon Research, Inc. in Lawrenceville and Princeton, New Jersey. This DOE Contract Period was from December 8, 1992 to December 7, 1994 and has been extended to September 30, 1995. The overall objective of this program is to produce liquid fuels from coal by direct liquefaction at a cost that is competitive with conventional fuels. Specifically, this continuous bench-scale program contains provisions to examine new ideas in areas such as: low temperature pretreatments, more effective catalysts, on-line hydrotreating, new coal feedstocks, other hydrogen sources, more concentrated coal feeds and other highly responsive process improvements while assessing the design and economics of the bench-scale results. This quarterly report covers work on Laboratory Scale Studies, Continuous Bench-Scale Operations, Technical Assessment and Project Management.

  13. Control of pyrite addition in coal liquefaction process

    DOEpatents

    Schmid, Bruce K.; Junkin, James E.

    1982-12-21

    Pyrite addition to a coal liquefaction process (22, 26) is controlled (118) in inverse proportion to the calcium content of the feed coal to maximize the C.sub.5 --900.degree. F. (482.degree. C.) liquid yield per unit weight of pyrite added (110). The pyrite addition is controlled in this manner so as to minimize the amount of pyrite used and thus reduce pyrite contribution to the slurry pumping load and disposal problems connected with pyrite produced slag.

  14. SLURRY PHASE IRON CATALYSTS FOR INDIRECT COAL LIQUEFACTION

    SciTech Connect

    Abhaya K. Datye

    1998-11-19

    This report describes research conducted to support the DOE program in indirect coal liquefaction. Specifically, they have studied the attrition behavior of iron Fischer-Tropsch catalysts, their interaction with the silica binder and the evolution of iron phases in a synthesis gas conversion process. The results provide significant insight into factors that should be considered in the design of catalysts for converting coal based syngas into liquid fuels.

  15. Slurry Phase Iron Catalysts for Indirect Coal Liquefaction

    SciTech Connect

    Abhaya K. Datye

    1998-09-10

    This report describes research conducted to support the DOE program in indirect coal liquefaction. Specifically, we have studied the attrition behavior of Iron Fischer-Tropsch catalysts, their interaction with the silica binder and the evolution of iron phases in a synthesis gas conversion process. The results provide significant insight into factors that should be considered in the design of catalysts for the conversion of coal-derived synthesis gas into liquid fuels.

  16. Coal-derived promoters for the liquefaction of Illinois coal. Technical report, September 1, 1991--November 30, 1991

    SciTech Connect

    Carty, R.H.

    1991-12-31

    The objective of this program is to investigate the use of liquids derived from coal either by mild gasification or supercritical extraction (SCE) to promote direct liquefaction of Illinois coal. Some organic sulfur-, nitrogen-, and oxygen-containing compounds have been found to enhance liquefaction reactions. The use of Illinois coal to produce liquid fractions rich in these types of compounds could increase the rates of liquefaction reactions, thus improving the process economics. An integrated process combining direct liquefaction with mild gasification or SCE of coal is being developed by IGT. The approach taken in this two-year program is to use recently developed molecular probe techniques to assess the reactivity of three coal-derived liquids with respect to (A) hydrogen transfer rate, (B) carbon-carbon bond cleavage rate, (C) free radical flux, and (D) hydrocracking activity. Sample liquids from Illinois Basin Coal IBC-106 are prepared by three methods: mild gasification in an isothermal free-fall reactor (IFFR), steam treatment followed by mild gasification in a fixed-bed reactor (ST/FBR), and SCE using toluene in a batch autoclave. During the first year of the program, the IFFR and ST/FBR coal liquids were produced and characterized, and the IFFR liquid was assessed by the four molecular-probe methods. During the first quarter of the second year, reactivity testing and data analysis on the ST/FBR coal liquid was completed. For the ST/FBR liquid, hydrogen transfer rate showed a mean increase of 7%, C-C bond cleavage selectivity increased by 27%, free radical flux increased 101%, and data indicated a 227% increase in hydrocracking activity. 12 refs., 5 figs., 7 tabs.

  17. SUMMARY REPORT OF THE DOE DIRECT LIQUEFACTION PROCESS DEVELOPMENT CAMPAIGN OF THE LATE TWENTIETH CENTURY

    SciTech Connect

    F.P. Burke; S.D. Brandes; D.C. McCoy; R.A. Winschel; D. Gray; G. Tomlinson

    2001-07-01

    Following the petroleum price and supply disruptions of 1973, the U.S. government began a substantial program to fund the development of alternative fuels. Direct coal liquefaction was one of the potential routes to alternative fuels. The direct coal liquefaction program was funded at substantial levels through 1982, and at much lower levels thereafter. Those processes that were of most interest during this period were designed to produce primarily distillate fuels. By 1999, U.S. government funding for the development of direct coal liquefaction ended. Now that the end of this campaign has arrived, it is appropriate to summarize the process learnings derived from it. This report is a summary of the process learnings derived from the DOE direct coal liquefaction process development campaign of the late twentieth century. The report concentrates on those process development programs that were designed to produce primarily distillate fuels and were largely funded by DOE and its predecessors in response to the petroleum supply and price disruptions of the 1970s. The report is structured as chapters written by different authors on most of the major individual DOE-funded process development programs. The focus of the report is process learnings, as opposed to, say, fundamental coal liquefaction science or equipment design. As detailed in the overview (Chapter 2), DOE's direct coal liquefaction campaign made substantial progress in improving the process yields and the quality of the distillate product. Much of the progress was made after termination by 1983 of the major demonstration programs of the ''first generation'' (SRC-II, H-Coal, EDS) processes.

  18. Advanced direct liquefaction concepts for PETC generic units

    SciTech Connect

    Not Available

    1992-04-01

    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.

  19. Integrated coal liquefaction, gasification and electricity production process

    SciTech Connect

    Cheng, S.

    1986-06-10

    A method is described for the physical and operational integration of a carbonaceous gasification plant, a gas fuel synthesis plant and a power generation station to economically produce synfuel and electric power consisting of: (a) producing synthesis gas comprising carbon monoxide and hydrogen from carbonaceous raw materials in a gasification unit under endothermic reaction conditions wherein the gasification unit utilizes exhaust steam from step (f) effective to provide at least a portion of the endothermic heat of reaction necessary for the reaction and wherein the gas from the gasification unit is passed to a coal liquefaction stage; (b) liquefying and hydrogenating coal under exothermic reaction conditions with the synthesis gas from the gasification unit as a source of hydrogen thereby producing a synthetic hydrocarbonaceous fuel and tail gases; (c) providing water to the liquefaction stage in an indirect heat exchange relationship to remove at least a portion of the exothermic heat of reaction from the coal liquefaction stage by generating high pressure steam from the water and passing the high pressure steam to a power generation unit; (d) continuously purging the tail gases from the liquefaction stage, feeding the tail gases to the power generation unit and burning the tail gases with or without additional fuel sources to superheat the high pressure steam; (e) passing the superheated steam to a turbine-generator means within the power generating unit to produce electricity and exhaust steam; and (f) feeding at least a portion of the exhaust steam from the power generating unit to the gasification unit.

  20. Activity and selectivity of molybdenum catalysts in coal liquefaction reactions

    SciTech Connect

    Curtis, C.W.; Pellegrino, J.L. )

    1988-01-01

    The purpose of this work is to evaluate how effectively three different molybdenum catalysts promote reactions involving heteroatom removal and cleavage of alkyl bridge hydrodeoxygenation (HDO), hydrodesulfurization (HDS), hydrodenitrogenation (HDN) and hydrocracking (HYC). Both model and coal liquefaction reactions were performed to test the activity and selectivity of three different molybdenum catalysts. The three catalysts used were molybdenum naphthenate, molybdenum supported on gamma alumina (Mo/Al{sub 2}O{sub 3}) and precipitated, poorly crystalline molybdenum disulfide (MoS{sub 2}). The model compounds, chosen to mimic coal structure, on which the effectiveness of the catalysts for the model reactions was tested were: 1-methylnaphthalene, representing aromatic hydrocarbons, for hydrogenation; 1-naphthol, representing oxygen containing compounds, for deoxygenation; benzothiophene, representing sulfur containing compounds, for desulfurization; indole, representing nitrogen containing compounds, for denitrogenation; and bibenzyl, representing alkyl bridging structures, for hydrocracking. Catalytic reactions of combinations of reactants were performed to simulate a complex coal matrix. Thermal and catalytic coal liquefaction reactions were performed using Illinois No. 6 coal with anthracene as a solvent. The efficacy of the catalysts was determined by comparing the product and compound class fractions obtained from the liquefaction reactions.

  1. Rationale for continuing R&D in indirect coal liquefaction

    SciTech Connect

    Gray, D.; Tomlinson, G.

    1995-12-31

    The objective of this analysis is to use the world energy demand/supply model developed at MITRE to examine future liquid fuels supply scenarios both for the world and for the United States. This analysis has determined the probable extent of future oil resource shortages and the likely time frame in which the shortages will occur. The role that coal liquefaction could play in helping to alleviate this liquid fuels shortfall is also examined. The importance of continuing R&D to improve process performance and reduce the costs of coal-derived transportation fuel is quantified in terms of reducing the time when coal liquids will become competitive with petroleum.

  2. Coal liquefaction in an inorganic-organic medium

    DOEpatents

    Vermeulen, Theodore; Grens, II, Edward A.; Holten, Ronald R.

    1982-01-01

    Improved process for liquefaction of coal by contacting pulverized coal in an inorganic-organic medium solvent system containing a ZnCl.sub.2 catalyst, a polar solvent with the structure RX where X is one of the elements O, N, S or P, and R is hydrogen or a lower hydrocarbon radical; the solvent system can contain a hydrogen donor solvent (and must when RX is water) which is immiscible in the ZnCl.sub.2 and is a hydroaromatic hydrocarbon, selected from tetralin, dihydrophenanthrene, dihydroanthracene or a hydrogenated coal derived hydroaromatic hydrocarbon distillate fraction.

  3. Donor solvent coal liquefaction with bottoms recycle at elevated pressure

    DOEpatents

    Bauman, Richard F.; Taunton, John W.; Anderson, George H.; Trachte, Ken L.; Hsia, Steve J.

    1982-01-01

    An improved process for liquefying solid carbonaceous materials wherein increased naphtha yields are achieved by effecting the liquefaction at a pressure within the range from about 1750 to about 2800 psig in the presence of recycled bottoms and a hydrogen-donor solvent containing at least 0.8 wt % donatable hydrogen. The liquefaction is accomplished at a temperature within the range from about 700.degree. to about 950.degree. F. The coal:bottoms ratio in the feed to liquefaction will be within the range from about 1:1 to about 5:1 and the solvent or diluent to total solids ratio will be at least 1.5:1 and preferably within the range from about 1.6:1 to about 3:1. The yield of naphtha boiling range materials increases as the pressure increases but generally reaches a maximum at a pressure within the range from about 2000 to about 2500 psig.

  4. A characterization and evaluation of coal liquefaction process streams. Quarterly technical progress report, October 1--December 31, 1994

    SciTech Connect

    Robbins, G.A.; Brandes, S.D.; Winschel, R.A.; Burke, F.P.

    1995-05-01

    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. During this quarter, analyses were completed on 65 process samples from representative periods of HRI Run POC-2 in which coal, coal/plastics, and coal/rubber were the feedstocks. A sample of the oil phase of the oil/water separator from HRI Run POC-1 was analyzed to determine the types and concentrations of phenolic compounds. Chemical analyses and microautoclave tests were performed to monitor the oxidation and measure the reactivity of the standard coal (Old Ben Mine No. 1) which has been used for the last six years to determine solvent quality of process oils analyzed in this and previous DOE contracts.

  5. Advanced liquefaction using coal swelling and catalyst dispersion techniques. Quarterly technical progress report, April--June 1992

    SciTech Connect

    Curtis, C.W.; Gutterman, C.; Chander, S.

    1992-08-26

    Research in this project centers upon developing a new approach to the direct liquefaction of coal to produce an all-distillate product slate at a sizable cost reduction over current technology. The approach integrates all aspects of the coal liquefaction process including coal selection, pretreatment, coal swelling with catalyst impregnation, coal liquefaction experimentation, product recovery with characterization, alternate bottoms processing, and a technical assessment including an economic evaluation. The project is being carried out under contract to the United States Department of Energy. On May 28, 1992, the Department of Energy authorized starting the experimental aspects of this projects; therefore, experimentation at Amoco started late in this quarterly report period. Research contracts with Auburn University, Pennsylvania State University, and Foster Wheeler Development Corporation were signed during June, 1992, so their work was just getting underway. Their work will be summarized in future quarterly reports. A set of coal samples were sent to Hazen Research for beneficiation. The samples were received and have been analyzed. The literature search covering coal swelling has been up-dated, and preliminary coal swelling experiments were carried out. Further swelling experimentation is underway. An up-date of the literature on the liquefaction of coal using dispersed catalysts is nearing completion; it will be included in the next quarterly report.

  6. Construction of a 150 t/d pilot plant for bituminous coal liquefaction

    SciTech Connect

    Ishibashi, Hirohito; Kobayashi, Masatoshi; Suzuki, Satoru

    1994-12-31

    This present paper covers bituminous coal liquefaction R and D carried out by Nippon Coal Oil Co., Ltd. (NCOL). Construction of a 150 ton/day bituminous coal liquefaction pilot plant will be presented. The NEDOL process is characterized by the wide applicability of various coal grades, such as low-rank bituminous coal, subbituminous coal and low-rank subbituminous coal, and a single-stage liquefaction method that combines the advantages of a hydrogen-donor solvent and a fine iron catalyst. A vacuum distillation system for solid-liquid separation is used to improve reliability. The simplicity of this process ensures a high degree of stability.

  7. Design, synthesis, and characterization of novel fine-particle, unsupported catalysts for coal liquefaction

    SciTech Connect

    Klein, M.T.

    1991-12-30

    The purpose of this work is to investigate the kinetics-assisted design, synthesis and characterization of fme-pardcle, unsupported catalysts for coal liquefaction. The goal is to develop a fundamental understanding of coal catalysis and catalysts that will, in turn, allow for the specification of a novel optimal catalyst for coal liquefaction.

  8. Coal liquefaction. Quarterly report, January-March 1979. [US DOE supported

    SciTech Connect

    1980-01-01

    Progress in DOE-supported coal liquefaction pilot plant projects is reported: company, location, contract, funding, process description, history and progress in the current quarter. Related projects discussed are: coking and gasification of liquefaction plant residues, filtration of coal liquids and refining of coal liquids by hydrogenation. (LTN)

  9. Design, synthesis, and characterization of novel fine-particle, unsupported catalysts for coal liquefaction

    SciTech Connect

    Klein, M.T.; Foley, H.C.

    1992-03-23

    The purpose of this work is to investigate the kinetics-assisted design, synthesis and characterization of fine-particle, unsupported catalysts for coal liquefaction. The goal is to develop a fundamental understanding of coal catalysis and catalysts that will, in turn, allow for the specification of a novel optical catalyst for coal liquefaction.

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

    SciTech Connect

    Robbins, G.A.; Brandes, S.D.; Winschel, R.A.; Burke, F.P.

    1995-12-01

    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.

  11. Advanced liquefaction using coal swelling and catalyst dispersion techniques. Volume 1, Final technical report, October 1, 1991--September 30, 1994

    SciTech Connect

    Curtis, C.W.; Gutterman, C.; Chander, S.

    1994-12-31

    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 solvents were used. Noncatalytic reactions showed no benefit from SO{sub 2} treatment. Coupling coal swelling and SO{sub 2} treatment with slurry catalysts was also not beneficial, although high conversion was seen with continuous operation and long residence time, however, similar high conversion was observed with untreated coal. SO{sub 2} treatment is not economically attractive unless it provides about 17% increase in coal reactivity. In most cases, the best results were obtained when the coal was untreated and the slurry catalyst was added directly into the reactor. Foster Wheeler`s ASCOT process had better average liquid yields than either Wilsonville`s vacuum tower/ROSE combination or delayed coking process. This liquid product also had good quality.

  12. Exxon donor solvent (EDS) coal liquefaction process development program status (at the beginning of 1980)

    SciTech Connect

    Epperly, W.R.; Plumlee, K.W.; Wade, D.T.

    1980-01-01

    A discussion covers a brief process description; typical yield responses to changes in liquefaction process variables; product flexibility achieved by liquefaction bottoms recycle or processing via the Flexicoking process and/or partial oxidation; potential product utilization schemes, including direct uses and various upgrading options; the EDS project schedule for 1977-83, including the expected startup of the 250 ton/day liquefaction pilot plant in May 1980 and a 70 ton/day Flexicoking prototype unit in Feb. 1982; and the results of a recent cost study which showed that an EDS plant incorporating Flexicoking and partial oxidation of the bottoms (without recycling) to convert 28,000 tons/day of Illinois No. 6 coal to 62,000 bbl/day fuel oil equivalent of product would involve an investment of $3.7 billion and a required initial selling price for the C/sub 3/ plus liquid product of $48/bbl, based on 100% equity financing.

  13. Direct liquefaction proof-of-concept program. Finaltopical report, Bench Run 4 (227-95)

    SciTech Connect

    Comolli, A.G.; Pradhan, V.R.; Lee, T.L.K.

    1997-03-01

    This report presents the results of bench-scale work, Bench Run PB-04, conducted under the DOE Proof of Concept-Bench Option Program in direct coal liquefaction at Hydrocarbon Technologies, Inc. in Lawrenceville, New Jersey. The Bench Run PB-04 was the fifth of the nine runs planned in the POC Bench Option Contract between the U.S. DOE and Hydrocarbon Technologies, Inc. Bench Run PB-04 had multiple goals. These included the evaluation of the effects of dispersed slurry catalyst system on the performance of direct liquefaction of a subbituminous Wyoming Black Thunder mine coal under extinction recycle (454{degrees}C+ recycle) condition; another goal was to investigate the effects of the combined processing of automobile shredder residue (auto-fluff) with coal and other organic waste materials. PB-04 employed a two-stage, back-mixed, slurry reactor system with an interstage V/L separator and an in-line fixed-bed hydrotreater. The HTI`s newly modified P/Fe catalyst was very effective for direct liquefaction and coprocessing of Black Thunder mine subbituminous coal with Hondo resid and auto-fluff; during `coal-only` liquefaction mode, over 93% maf coal conversion was obtained with about 90% residuum conversion and as high as 67% light distillate (C{sub 4}-975 F) yield, while during `coprocessing` mode of operation, distillate yields varied between 58 and 69%; the residuum conversions varied between 74 and 89% maf. Overall, it is concluded, based upon the yield data available from PB-04, that auto-effective as MSW plastics in improving coal hydroconversion process performance. Auto-fluff did not increase light distillate yields nor decrease light gas make and chemical hydrogen consumption in coal liquefaction, as was observed to occur with MSW plastics.

  14. Process for manufacture of solvent for coal liquefaction

    SciTech Connect

    Chikata, T.; Nishioka, K.; Sasaki, K.; Sunami, Y.

    1981-12-01

    A solvent useful in coal liquefaction is obtained by separating the heavy liquid resulting from coal liquefaction into a fraction boiling at temperatures of between 200/sup 0/ and 210/sup 0/ C, a fraction boiling at temperatures between 211/sup 0/ and 250/sup 0/ C, and a fraction boiling at not less than 250/sup 0/ C, subjecting the fraction boiling at between 211/sup 0/ C and 250/sup 0/ C to two hydrogenation treatments, mixing the hydrogenated product with the fraction boiling at between 200/sup 0/ and 210/sup 0/ C which optionally has been hydrogenated to form a resultant mixture and mixing a portion of the resultant mixture with the fraction boiling at not less than 250/sup 0/ C which has been optionally hydrogenated.

  15. A characterization and evaluation of coal liquefaction process streams. Quarterly technical progress report, October 1--December 31, 1995

    SciTech Connect

    Robbins, G.A.; Brandes, S.D.; Winschel, R.A.; Burke, F.P.

    1996-05-01

    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. During this reporting period, CONSOL completed analyses of 81 feed and process stream samples from HTI bench Run CMSL-9. HTI liquefaction bench unit Run CMSL-9 (227-87) was operated with all-dispersed catalyst and Black Thunder Mine (Wyodak and Anderson seam) coal, with and without mixed plastics or high density polyethylene (HDPE) as coprocessing feedstocks. The dispersed catalysts used were Molyvan A and HTI`s iron catalyst, a sulfated iron hydroxide. Results are discussed in this report.

  16. Advanced Coal Liquefaction Research and Development Facility, Wilsonville, Alabama

    SciTech Connect

    Not Available

    1992-01-01

    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 used as slurry catalyst at a rate of 2 wt % MF coal throughout the run. (TNPS was the sulfiding agent.)

  17. A Characterization and Evaluation of Coal Liquefaction Process Streams

    SciTech Connect

    1998-10-01

    An updated assessment of the physico-chemical analytical methodology applicable to coal-liquefaction product streams and a review of the literature dealing with the modeling of fossil-fuel resid conversion to product oils are presented in this document. In addition, a summary is provided for the University of Delaware program conducted under this contract to develop an empirical test to determine relative resid reactivity and to construct a computer model to describe resid structure and predict reactivity.

  18. Process for coal liquefaction using electrodeposited catalyst

    DOEpatents

    Moore, Raymond H.

    1978-01-01

    A process for the liquefaction of solid hydrocarbonaceous materials is disclosed. Particles of such materials are electroplated with a metal catalyst and are then suspended in a hydrocarbon oil and subjected to hydrogenolysis to liquefy the solid hydrocarbonaceous material. A liquid product oil is separated from residue solid material containing char and the catalyst metal. The catalyst is recovered from the solid material by electrolysis for reuse. A portion of the product oil can be employed as the hydrocarbon oil for suspending additional particles of catalyst coated solid carbonaceous material for hydrogenolysis.

  19. Fundamental studies of retrograde reactions in direct liquefaction

    SciTech Connect

    Serio, M.A.; Solomon, P.R.; Kroo, E.; Charpenay, S.; Bassilakis, R.

    1990-01-01

    Research on coal liquefaction continued. We have tried to get definitive structural information on the C-C-O polymers, (poly(4-allylphenol)) from a variety of analytical techniques. However, in all cases the results were not conclusive. In view of the need for a better characterization of the model polymers before drawing definitive conclusions from liquefaction of pyrolysis results, we have reexamined some of the previous analyses and have conducted further characterization of the C-C-O polymers by elemental analysis and FT-IR spectroscopy. Liquefaction experiments were repeated at 400{degree}C, 10 minutes for the three raw coals. For the Zap and Illinois coals, the results at 10 minutes were significantly different when compared to the first set of experiments. Since all of these experiments were done shortly before the heater elements failed in the Fluidized Sand Bath (FSB), it was thought that this may have been a contributing factor, since the reproducibility in the past has been quite good for the 30 minute experiments ({plus minus}3%). The FSB was rebuilt and liquefaction experiments were repeated for a second time at 400{degree}C, 10 minutes for the three raw coals. The results were now in general agreement with the results of the previous set. Work continued on using the AFR FG-DVC liquefaction model to predict the results of the experiments on coals and modified coals from this program. 3 refs., 3 figs.

  20. Coal liquefaction to increase jet fuel production

    NASA Technical Reports Server (NTRS)

    1979-01-01

    Processing concept that increases supply of jet fuel has been developed as part of study on methods for converting coal to hydrogen, methane, and jet fuel. Concept takes advantage of high aromatic content of coal-derived liquids to make high-octane gasoline, instead of destroying aromatics to make jet fuel.

  1. Status of the development of EDS coal liquefaction

    SciTech Connect

    Vick, G.K.; Epperly, W.R.

    1982-07-23

    This article traces the evolution and development of a modern coal liquefaction technology, the EDS (Exxon Donor Solvent) process, over a period of 15 years. During this time the technology has been advanced from laboratory experiments to a pilot plant with a coal feed rate of 250 tons per day, and findings from several areas of science and technology have been important. The process is now in the final stage of development to generate the data needed to design a plant of commercial size.

  2. Effect of dispersing agent in heating process for high dispersion of coal liquefaction catalyst

    SciTech Connect

    Okada, Y.; Haneda, M.; Inokuchi, K.; Aihara, Y.; Imada, K.; Kai, T.; Sakaki, T.; Shibata, M.

    1999-07-01

    This work deals with one proposal concerning the improvement of catalytic activity on coal liquefaction. It is known that pyrite (FeS{sub 2}) transform into pyrrhotite (Fe{sub 1{minus}x}S) and aggregate at the heating process on coal liquefaction. The aggregation of liquefaction catalyst decreases the specific surface area, and causes the decline in catalytic activity. The authors investigated the effects of dispersing agent on the morphological change and the dispersing state of liquefaction catalyst at the rapid heating process. For the liquefaction tests with added dispersing agent, the product yields were compared with the results of other tests.

  3. Surface modified coals for enhanced catalyst dispersion and liquefaction

    SciTech Connect

    Dr. Yaw D. Yeboah

    1998-10-29

    The aim of the study is to enhance catalyst loading and dispersion in coal for improved liquefaction by preadsorption of surfactants and catalysts on to the coal. During this reporting period, zeta potential measurements were conducted to assess the surface charge on the raw, pretreated and catalyzed coal samples. The surface area, transmission spectroscopy and luminescence intensity of the raw coal and pretreated coal samples were also determined to assess the quality of the coal surface. Across a broad range of pH values, the raw coal had an overall negative charge. Coal treated with anionic surfactant SDS maintained an overall net negative surface negative charge. The interaction between the coal and cationic surfactant DDAB caused the opposite effect resulting in a more positive coal surface charge. Although one would have expected little or no effect of the neutral surfactant Triton X-100, there appears to be some difference in the results of the raw coal and the coal treated with Triton X-100. The authors believe that the Triton not only binds to the nonpolar sites but also has a strong affinity for the polar sites through electrostatic bonding and interaction between the hydrophobic tails. The addition of molybdenum to coal pretreated with DDAB caused a reduction in the positive charge of the coal surface probably due to possible ionic interaction between the coal surface, the surfactant and the catalyst. The adsorption isotherm of the coal was characteristic of isotherms for porous samples and the surface area of the coal increased from 30 m{sup 2}/g to 77 m{sup 2}/g when washed with deionized water. This suggests coal washing may be one method of increasing the surface area for surfactant adsorption. Although the transmission measurements provided valuable information about the coal it resulted in little information on the amount of adsorbed Triton. However, the maximum solid-liquid ratio for optimum surfactant loading of Triton X-100 was determined via

  4. Coal liquefaction technology. (Latest citations from the NTIS Bibliographic database). Published Search

    SciTech Connect

    1996-09-01

    The bibliography contains citations concerning the technologies and processes for converting coal to liquid chemicals and fuels. Topics include materials characterization of liquefaction processes, catalysis, pyrolysis, depolymerization, coprocessing, and integrated liquefaction. Also discussed are liquid fuel use in automobiles and power generation, low-temperature carbonization technology, multi-stage liquefaction, cost benefit analysis, and commercialization of liquefaction technology. (Contains 50-250 citations and includes a subject term index and title list.) (Copyright NERAC, Inc. 1995)

  5. Microbial recovery of metals from spent coal liquefaction catalysts. Quarterly report, July--September 1993

    SciTech Connect

    Sandbeck, K.A.; Joffe, P.M.

    1993-12-31

    The project objectives outlined in the previous reports involved defining conditions and cultures best suited to achieve the most effective metal release from spent coal liquefaction catalysts by microbial processes. The work initiated in the first quarter of 1993 was continued and expanded using solvent extraction systems defined by the multiple solvent tests used for washing the catalysts. To reduce the number of solvent systems the data were examined and two solvents selected for continued testing. The two solvent systems which were chosen and have been employed are the isopropanol and a tetrahydrofuran (THF) extractive solvents. In the present simplified extractive system, the catalysts are washed with the solvent with simple agitation to prevent catalyst breakage. Studies on the effect of catalyst surface area will be continued in conjunction with the progressive development of the optimized microbial metal releasing system. Thermophilic cultures (Bacillus stearothermophilus and Metallosphaera sedula) are being grown at 60 C for initial metal releasing studies. Since THF has proven to be a superior solvent system as judged by metal release, research has concentrated on using THF as the solvent system allowing work to proceed rapidly. However, additional work will still be directed toward defining any solvent system superior to THF in terms of aiding microbiological release of metals and economic feasibility. These studies include measurements of metal release at various catalyst-media ratios for both the tetrahydrofuran and isopropanol washed catalysts. The importance of the catalyst-media ratios is assuming a greater importance since it is desired to reduce the media volume to the lowest level possible while still retaining good metals release.

  6. System for analyzing coal liquefaction products

    DOEpatents

    Dinsmore, Stanley R.; Mrochek, John E.

    1984-01-01

    A system for analyzing constituents of coal-derived materials comprises three adsorption columns and a flow-control arrangement which permits separation of both aromatic and polar hydrocarbons by use of two eluent streams.

  7. Highly dispersed catalysts for coal liquefaction. Phase 1 final report, August 23--November 22, 1994

    SciTech Connect

    Hirschon, A.S.; Wilson, R.B.; Ghaly, O.

    1995-03-22

    The ultimate goal of this project is to develop novel processes for making the conversion of coal into distillable liquids competitive to that of petroleum products in the range of $25/bbl. The objectives of Phase 1 were to determine the utility of new precursors to highly dispersed catalysts for use of syngas atmospheres in coal liquefaction, and to estimate the effect of such implementation on the cost of the final product. The project is divided into three technical tasks. Tasks 1 and 2 are the analyses and liquefaction experiments, respectively, and Task 3 deals with the economic effects of using these methods during coal liquefaction. Results are presented on the following: Analytical Support--screening tests and second-stage conversions; Laboratory-Scale Operations--catalysts, coal conversion in synthetic solvents, Black Thunder screening studies, and two-stage liquefaction experiments; and Technical and economic Assessment--commercial liquefaction plant description, liquefaction plant cost; and economic analysis.

  8. ENVIRONMENTAL ASSESSMENT DATA BASE FOR COAL LIQUEFACTION TECHNOLOGY: VOLUME II. SYNTHOIL, H-COAL, AND EXXON DONOR SOLVENT PROCESSES

    EPA Science Inventory

    This volume is an environmental characterization of three selected coal liquefaction systems: Synthoil, H-Coal, and Exxon Donor Solvent. It documents and evaluates existing environmentally significant data. System characterization includes an integrated multimedia assessment of d...

  9. Low severity coal liquefaction promoted by cyclic olefins

    SciTech Connect

    Curtis, C.W.

    1992-07-27

    Low severity coal liquefaction allows for solubilization of coal with reduced gas make. These lower severity conditions may result in some selective bond rupture. Promotion of coal solubilization through hydrogen transfer using highly active and effective hydrogen donors is the objective of this study. The highly effective donors being tested are cyclic olefins. Representative cyclic olefins are isotetralin, which is 1,4,5,8-tetrahydronaphthalene, and 1,4,5,8,9,10-hexahydroanthracene. These compounds are hydroaromatics without aromatic rings and have been shown to be highly effective donors. The objective of the work performed in this study during this quarter was to evaluate reaction parameters for low severity liquefaction reactions using the cyclic olefin, hexahydroanthracene, and the aromatic, anthracene. These model compounds were reacted under a variety of conditions to evaluate their reactivity without coal. The reactions were performed under both thermal and catalytic conditions. Finely divided catalysts from different molybdenum precursors were used to determine their activity in promoting hydrogenation and hydrogen transfer at low severity conditions. The catalysts used were Molyvan L, sulfurized oxymolybdenum dithiocarbamate, molybdenum naphthenate, and Molyvan 822, organo molybdenum dithiocarbamate.

  10. The Dual Role of Oxygen Functions in Coal Pretreatment and Liquefaction: Crosslinking and Cleavage Reactions

    SciTech Connect

    Michael Serio; Erik Kroo; Sylvie Charpenay; Peter Solomon

    1993-09-30

    The overall objective of this project was to elucidate and model the dual role of oxygen functions in thermal pretreatment and liquefaction of low rank coals through the application of analytical techniques and theoretical models. The project was an integrated study of model polymers representative of coal structures, raw coals of primarily low rank, and selectively modified coals in order to provide specific information relevant to the reactions of real coals. The investigations included liquefaction experiments in microautoclave reactors, along with extensive analysis of intermediate solid, liquid and gaseous products. Attempts were made to incorporate the results of experiments on the different systems into a liquefaction model.

  11. Two-stage, closed coupled catalytic liquefaction of coal. Sixteenth quarterly report, 1 July 1992--30 September 1992

    SciTech Connect

    Comolli, A.G.; Johanson, E.S.; Karolkiewicz, W.F.; Lee, L.K.; Stalzer, R.H.

    1992-12-01

    This quarterly report covers activities of the Two-Stage, Close-Coupled Catalytic Liquefaction of Coal Program during the period of July 1--September 30, 1992, at Hydrocarbon Research, Inc., in Lawrenceville and Princeton, New Jersey. This DOE contract period is from October 1, 1998 to December 31, 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, Bench Scale Studies and PDU Activities focusing on scale-up of the Catalytic Two-Stage Liquefaction (CTSL) processing of sub-bituminous Black Thunder Coal.

  12. ANALYTICAL METHODS FOR HAZARDOUS ORGANICS IN LIQUID WASTES FROM COAL GASIFICATION AND LIQUEFACTION PROCESSES

    EPA Science Inventory

    This study was conducted by the University of Southern California group to provide methods for the analysis of coal liquefaction wastes from coal conversion processing plants. Several methods of preliminary fractionation prior to analysis were considered. The most satisfactory me...

  13. Design of generic coal conversion facilities: Indirect coal liquefaction, Fischer-Tropsch synthesis

    SciTech Connect

    Not Available

    1991-10-01

    A comprehensive review of Fischer-Tropsch (F-T) technology, including fixed, fluidized, and bubble column reactors, was undertaken in order to develop an information base before initiating the design of the Fischer-Tropsch indirect liquefaction PDU as a part of the Generic Coal Conversion Facilities to be built at the Pittsburgh Energy Technology Center (PETC). The pilot plant will include a fixed bed and slurry bubble column reactor for the F-T mode of operation. The review encompasses current status of both these technologies, their key variables, catalyst development, future directions, and potential improvement areas. However, more emphasis has been placed on the slurry bubble column reactor since this route is likely to be the preferred technology for commercialization, offering process advantages and, therefore, better economics than fixed and fluidized bed approaches.

  14. Two-stage, close coupled catalytic liquefaction of coal. Fourteenth quarterly report, 1 January 1992--31 March 1992

    SciTech Connect

    Comolli, A.G.; Johanson, E.S.; Lee, T.L.K.; Popper, G.A.; Stalzer, R.H.

    1992-04-01

    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.

  15. Mechanism of hydrogen incorporation in coal liquefaction. Quarterly progress report, April 1995--June 1995

    SciTech Connect

    1995-09-01

    Mechanisms important to coal liquefaction and hydrogen transfer in coal liquefaction are being investigated. We continued our studies of the reactions of various organic compounds with D{sub 2}. Also described in this report is the success of hydrogenating naphthalene utilizing silica as a catalyst.

  16. Coal liquefaction process streams characterization and evaluation: Application of liquid chromatographic separation methods to THF-soluble portions of integrated two-stage coal liquefaction resids

    SciTech Connect

    Green, J.B.; Pearson, C.D.; Young, L.L.; Green, J.A. )

    1992-05-01

    This study demonstrated the feasibility of using non-aqueous ion exchange liquid chromatography (NIELC) for the examination of the tetrahydrofuran (THF)-soluble distillation resids and THF-soluble whole oils derived from direct coal liquefaction. The technique can be used to separate the material into a number of acid, base, and neutral fractions. Each of the fractions obtained by NIELC was analyzed and then further fractionated by high-performance liquid chromatography (HPLC). The separation and analysis schemes are given in the accompanying report. With this approach, differences can be distinguished among samples obtained from different process streams in the liquefaction plant and among samples obtained at the same sampling location, but produced from different feed coals. HPLC was directly applied to one THF-soluble whole process oil without the NIELC preparation, with limited success. The direct HPLC technique used was directed toward the elution of the acid species into defined classes. The non-retained neutral and basic components of the oil were not analyzable by the direct HPLC method because of solubility limitations. Sample solubility is a major concern in the application of these techniques.

  17. Coal liquefaction process with increased naphtha yields

    SciTech Connect

    Ryan, D.F.

    1986-08-12

    A process is described for liquefying solid carbonaceous materials comprising the steps of: (a) forming a slurry of finely divided solid carbonaceous material and a suitable solvent of diluent; (b) subjecting the slurry from step (a) to liquefaction at an elevated temperature and pressure in the presence of molecular hydrogen to produce a normally gaseous product, a normally liquid product and a normally solid bottoms product; (c) separating the product from step (b) into a gas phase, a liquid phase and a normally solid phase and further separating the liquid portion of the product into a naphtha boiling range product; (d) combining from about 5 wt% to about 20 wt% of the solvent boiling range product with from about 50 wt% to about 100 wt% of the vacuum gas-oil boiling range product and passing the mixture first to a hydrotreater and then to a catalytic cracker; (e) separating the product from the catalytic cracker into a naphtha boiling range product and a solvent boiling range product; (f) combining the solvent boiling range product from the catalytic cracker with the solvent boiling range materials separated from the liquid product; and (g) hydrotreating the combined solvent boiling range streams.

  18. Low severity coal liquefaction promoted by cyclic olefins. Quarterly report, April--June 1993

    SciTech Connect

    Curtis, C.W.

    1993-11-01

    Low-severity coal liquefaction allows for the solubilization of coal with reduced gas make. The idea being tested in this research is whether selective bond rupture occurs during liquefaction at low temperatures that can be satisfied by hydrogen donation from highly active hydrogen donor compounds. Promotion of coal solubilization through hydrogen transfer using highly active and effective hydrogen donors is the objective of this study. The highly effective hydrogen donors being tested are cyclic olefins. Representative cyclic olefins are isotetralin (ISO), which is 1,4,5,8-tetrahydronaphthalene, and 1,4,5,8,9,10-hexahydroanthracene (HHA). These compounds have been shown to highly effective donors (Bedell and Curtis, 1991) which release their hydrogen at fairly low temperatures, in the 200 to 300{degree}C range. ISO has been shown to be much more effective than its hydroaromatic analogue tetralin (TET) in releasing hydrogen at low temperatures and transferring that hydrogen to an acceptor molecule or to coal (Bedell and Curtis, 1991). Likewise, at 380{degree}C, the ability of HHA to release hydrogen in both N{sub 2} and H{sub 2} atmospheres was greater than a comparative hydroaromatic compound, dihydroanthracene (DHA). However, when an acceptor molecule or coal was present, DHA was as or more active than HHA in transferring hydrogen (Bedell et al., 1993). In another study, at equivalent reaction conditions and in the presence of anthracene (ANT) as a hydrogen acceptor, ISO released more than 200 times as much hydrogen as TET and HHM released 18 to 25 times as much hydrogen as DHA (Wang, 1992).

  19. Low severity coal liquefaction promoted by cyclic olefins. Quarterly report, July--September 1993

    SciTech Connect

    Curtis, C.W.

    1993-12-31

    Low-severity coal liquefaction allows for the solubilization of coal with reduced gas make. The idea being tested in this research is whether selective bond rupture occurs during liquefaction at low temperatures that can be satisfied by hydrogen donation from highly active hydrogen donor compounds. Promotion of coal solubilization through hydrogen transfer using highly active and effective hydrogen donors is the objective of this study. The highly effective hydrogen donors being tested are cyclic olefins. Representative cyclic olefins are isotetralin (ISO), which is 1,4,5,8-tetrahydronaphthalene, and 1,4,5,8,9, 10hexahydroanthracene (HHA). These compounds have been shown to highly effective donors (Bedell and Curtis, 1991) which release their hydrogen at fairly low temperatures, in the 200 to 300{degrees}C range. ISO has been shown to be much more effective than its hydroaromatic analogue tetralin (TET) in releasing hydrogen at low temperatures and transferring that hydrogen to an acceptor molecule or to coal (Bedell and Curtis, 1991). Likewise, at 380{degrees}C, the ability of HHA to release hydrogen in both N{sub 2} and H{sub 2} atmospheres was greater than a comparative hydroaromatic compound, dihydroanthracene (DHA). However, when an acceptor molecule or coal was present, DHA was as or more active than HHA in transferring hydrogen (Bedell et al., 1993). In another study, at equivalent reaction conditions and in the presence of anthracene (ANT) as a hydrogen acceptor, ISO released more than 200 times as much hydrogen as TET and HHA released 18 to 25 times as much hydrogen as DHA (Wang, 1992).

  20. Microbial recovery of metals from spent coal liquefaction catalysts. Final and quarterly report, July 1994--September 1994

    SciTech Connect

    Sandbeck, K.A.; Cleveland, D.

    1995-08-01

    Research is reported on the recovery of molybdenum and nickel from spent coal liquefaction catalysts. Mo release from spent coal liquefaction catalysts has been shown to be dependent upon many parameters, but release is dominated by microbial growth. The microbial Mo release is a rapid process requiring less than one week for 90% of the releaseable Mo to be solubilized from whole washed (THF) catalyst. It could be expected that the rates would be even greater with crushed catalyst. Efforts were centered on optimizing the parameters that stimulate microbial growth and action and further efforts centered on catalyst pre-treatment prior to microbial bio-leaching. Recent experiments suggest that hydrogen peroxide promises to be an effective pre-treatment wash. Hydrogen peroxide was also found to be an effective and economical agent for metals solubilization per se and could promote solubilization without subjecting the catalyst to microbial growth.

  1. ADVANCED DIRECT LIQUEFACTION CONCEPTS FOR PETC GENERIC UNITS

    SciTech Connect

    Adam J. Berkovich

    2001-08-01

    The results of Laboratory and Bench-Scale experiments and supporting technical and economic assessments conducted under DOE Contract No. DE-AC22-91PC91040 are reported for the period April 1, 2001 to June 30 2001. This work involves the introduction into the basic two-stage liquefaction process several novel concepts, which include dispersed lower-cost catalysts, coal cleaning by oil agglomeration, and distillate hydrotreating and dewaxing. This project has been modified to include an investigation into the production of value added materials from coal using low-severity liquefaction based technologies.

  2. ADVANCED DIRECT LIQUEFACTION CONCEPTS FOR PETC GENERIC UNITS

    SciTech Connect

    Adam J. Berkovich

    2001-11-01

    The results of Laboratory and Bench-Scale experiments and supporting technical and economic assessments conducted under DOE Contract No. DE-AC22-91PC91040 are reported for the period July 1, 2001 to September 30 2001. This work involves the introduction into the basic two-stage liquefaction process several novel concepts, which include dispersed lower-cost catalysts, coal cleaning by oil agglomeration, and distillate hydrotreating and dewaxing. This project has been modified to include an investigation into the production of value added materials from coal using low-severity liquefaction based technologies.

  3. ADVANCED DIRECT LIQUEFACTION CONCEPTS FOR PETC GENERIC UNITS

    SciTech Connect

    Adam J. Berkovich

    2001-04-01

    The results of Laboratory and Bench-Scale experiments and supporting technical and economic assessments conducted under DOE Contract No. DE-AC22-91PC91040 are reported for the period January 1, 2001 to March 31 2001. This work involves the introduction into the basic two-stage liquefaction process several novel concepts, which include dispersed lower-cost catalysts, coal cleaning by oil agglomeration, and distillate hydrotreating and dewaxing. This project has been modified to include an investigation into the production of value added materials from coal using low-severity liquefaction based technologies.

  4. Power recovery system for coal liquefaction process

    DOEpatents

    Horton, Joel R.

    1985-01-01

    Method and apparatus for minimizing energy required to inject reactant such as coal-oil slurry into a reaction vessel, using high pressure effluent from the latter to displace the reactant from a containment vessel into the reaction vessel with assistance of low pressure pump. Effluent is degassed in the containment vessel, and a heel of the degassed effluent is maintained between incoming effluent and reactant in the containment vessel.

  5. Development of Highly Reactive Nanometer Fe-Based Catalysts for Coal Liquefaction

    SciTech Connect

    Franz, James A.; Linehan, John C.; Matson, Dean W.; Smurthwaite, Tricia D.; Bekhazi, Jacky; Alnajjar, Mikhail S.

    2008-03-01

    This paper describes research involving the liquefaction of coal and the removal of oxygen from coal product constituents. Subbituminous Coal and early stage coal liquefaction products contain a substantial fraction of hydroxy-substituted aromatic hydrocarbons (phenols). An important reaction for upgrading of coal-derived organic materials is to remove oxygen groups. This paper describes the hydro-deoxygenation of naphthols and the liquefaction of subbituminous Wyodak coal using a catalyst prepared by in-situ sulfidation of nanometer scale 6-line iron ferrihydrite. The FeS catalyst enables the conversion of naphthol in substantial yields to tetralin and naphthalene at 400 degrees C in 9,10-dihydrophenanthrene. The kinetics and procedures to observe coal liquefaction and hydro-deoxygenation, and the effects of in-situ sulfidation on conversion kinetics are described.

  6. A CHARACTERIZATION AND EVALUATION OF COAL LIQUEFACTION PROCESS STREAMS

    SciTech Connect

    G.A. Robbins; S.D. Brandes; D.J. Pazuchanics; D.G. Nichols; R.A. Winschel

    1999-02-01

    This is the Technical Progress Report for the sixteenth quarter of activities under DOE Contract No. DE-AC22-94PC93054. It covers the period April 1 through June 30, 1998. Described in this report are the following activities: (1) CONSOL characterized nine process stream samples received from Exxon Recycle Coal Liquefaction Unit (RCLU) operations conducted in 1994 with Rawhide Mine Wyoming subbituminous coal and all-dispersed Fe and Mo catalysts. (2) The University of Delaware subcontract related to resid reactivity was completed with issuance of the Topical Report covering work performed by Delaware. (3) Computational studies of the coal liquefaction resid models developed at the University of Delaware were continued at CONSOL R and D. The two reaction models, consisting of the reaction optimization and reaction once-through programs, were the focus of these studies. The updated resid structure data and results were used in the reaction models to predict percent conversion values that were compared with the experimentally-measured values from the University of Delaware. (4) Small samples of high-sulfur Hondo resid and anthracene oil were shipped to John Verkade of Iowa State University at his request. Verkade is testing a desulfurization method.

  7. Advanced Coal Liquefaction Research and Development Facility, Wilsonville, Alabama

    SciTech Connect

    Not Available

    1992-09-01

    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 Illinois No. 6 coal. Increasing viscosity and preasphaltenes made it difficult to operate at conditions similar to EXP-AO-60 catalyst operation, especially at lower catalyst replacement rates.

  8. Toxicity of a coal liquefaction product to aquatic organisms

    SciTech Connect

    Giddings, J.M.; Parkhurst, B.R.; Gehrs, C.W.; Millemann, R.E.

    1980-01-01

    As coal liquefaction processes approach commercialization in the United States, there is a growing need for information on their potential environmental impacts. Past oil spill experiences will not be adequate for predicting the effects of coal-derived oils, because the latter are chemically quite different from petroleum products. Using acute bioassay tests, a representative coal liquefaction product was compared with a petroluem-derived residual fuel oil and a diesel fuel, materials whose ecological effects have been documented following actual spills over the past 15 years. The acute toxicity of water soluble fractions (WSFs) of the three oils to two freshwater algae and one freshwater crustacean was determined. The WSFs were tested instead of the whole oils because (a) the water soluble components of an oil are responsible for most of its acute toxicity; and (b) while spilled oil can be contained and often recovered, the water with which it comes in contact will affect a larger area and for a longer time.

  9. Novel bimetallic dispersed catalysts for temperature-programmed coal liquefaction. Final report

    SciTech Connect

    Chunshan Song; Schobert, H.H.; Parfitt, D.P.

    1997-11-01

    Development of new catalysts is a promising approach to more efficient coal liquefaction. It has been recognized that dispersed catalysts are superior to supported catalysts for primary liquefaction of coals, because the control of initial coal dissolution or depolymerization requires intimate contact between the catalyst and coal. This research is a fundamental and exploratory study on catalytic coal liquefaction, with the emphasis on exploring novel bimetallic dispersed catalysts for coal liquefaction and the effectiveness of temperature-programmed liquefaction using dispersed catalysts. The primary objective of this research was to explore novel bimetallic dispersed catalysts from organometallic molecular precursors, that could be used in low concentrations but exhibit relatively high activity for efficient hydroliquefaction of coals under temperature-programmed conditions. We have synthesized and tested various catalyst precursors in liquefaction of subbituminous and bituminous coals and in model compound studies to examine how do the composition and structure of the catalytic precursors affect their effectiveness for coal liquefaction under different reaction conditions, and how do these factors affect their catalytic functions for hydrogenation of polyaromatic hydrocarbons, for cleavage of C-C bonds in polycyclic systems such as 4-(1-naphthylmethyl)bibenzyl, for hydrogenolysis of C-O bond such as that in dinaphthylether, for hydrodeoxygenation of phenolic compounds and other oxygen-containing compounds such as xanthene, and for hydrodesulfurization of polycyclic sulfur compounds such as dibenzothiophene. The novel bimetallic and monometallic precursors synthesized and tested in this project include various Mo- and Fe-based compounds.

  10. Release of heavy metals from sediment bed under wave-induced liquefaction.

    PubMed

    Sun, Zhenhong; Xu, Guohui; Hao, Ting; Huang, Zhe; Fang, Hongru; Wang, Gang

    2015-08-15

    Sediments in lakes and coasts can release metals into water via static diffusion and especially resuspension. The resuspension under sediment liquefaction may severely affect the concentrations of metals in water. In this study, flume experiments were carried out twice to study the release of two metal combinations (Zn and Pb; Zn and Cu), respectively. Each experiment included three phases: consolidation; non-liquefaction and liquefaction. Results showed that total Zn concentration at liquefaction phase increased by a maximum rate of 26 compared with the consolidation phase. The concentration of particulate Zn at liquefaction phase increased by a maximum rate of 8.30 compared with the non-liquefaction phase. The average concentration of dissolved Zn at the liquefaction phase increased up to 0.24 times from the consolidation phase. Total Zn concentration at the non-liquefaction phase increased by several times compared with the consolidation phase. Metals were homogeneously distributed in the liquefaction layer through wave actions. PMID:26111653

  11. Effects of low-temperature catalytic pretreatments on coal structure and reactivity in liquefaction

    SciTech Connect

    Song, C.; Huang, L.; Wenzel, K.; Saini, A.K.; Burgess, C.; Hatcher, P.G.; Schobert, H.H.

    1992-12-01

    During this quarterly period progress has been made in the following three subjects related to the effects of low-temperature thermal and catalytic pretreatments on coal structure and reactivity in liquefaction. First, the liquefaction behavior of three bituminous coals with a carbon content ranging from 77% to 85% was evaluated spectroscopically by [sup 13]C NMR and pyrolysis/gas chromatography/mass spectrometry to delineate the structural changes that occur in the coal during liquefaction. Complementary data includes ultimate and proximate analysis, along with optical microscopy for maceral determinations. Even though these are all bituminous coals they exhibit quite different physical and chemical characteristics. The coals vary in rank, ranging from HvC b to HvA b, in petrographic composition, different maceral percentages, and in chemical nature, percent of carbon and of volatiles. It is these variations that govern the products, their distribution, and conversion percentages. Some of the products formed can be traced to a specific maceral group. Second, pyrolysis-GC-MS and FTIR techniques were used to characterize Wyodak coal before and after drying in vacuum and in air and the residues from its thermal and catalytic liquefactions. The analysis of the air-dried coal shows a decrease in the phenolic type structures in the coal network and increase in the carbonyl structures as the oxidative drying proceeds. An enhanced decrease in the carbonyl structure is observed in the liquefaction residues from the raw coal as compared to that of the vacuum dried coal. The analyses of the liquefaction residues of the air-dried coal show an increase in the ether linkages which may have a negative impact on liquefaction. The extent of the solvent adduction also increases during liquefaction with the extent of oxidation of the coal. Finally, the effects of reaction conditions were investigated on conversion of low-rank coals using a Texas subbituminous coal.

  12. Coal liquefaction. Quarterly report, April-June 1979

    SciTech Connect

    1980-04-01

    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 with fourteen projects are described brieflly: funding, description, status, history, and progress in the current quarter. (LTN)

  13. Time phased alternate blending of feed coals for liquefaction

    DOEpatents

    Schweigharett, Frank; Hoover, David S.; Garg, Diwaker

    1985-01-01

    The present invention is directed to a method for reducing process performance excursions during feed coal or process solvent changeover in a coal hydroliquefaction process by blending of feedstocks or solvents over time. ,

  14. Direct liquefaction proof-of-concept program: Bench Run 05 (227-97). Final report

    SciTech Connect

    Comolli, A.G.; Pradhan, V.R.; Lee, T.L.K.; Karolkiewicz, W.F.; Popper, G.

    1997-04-01

    This report presents the results Bench Run PB-05, 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-05 was the fifth of the nine runs planned in the POC Bench Option Contract between the U.S. DOE and included the evaluation of the effect of using dispersed slurry catalyst in direct liquefaction of a high volatile bituminous Illinois No. 6 coal and in combined coprocessing of coal with organic wastes, such as heavy petroleum resid, MSW plastics, and auto-shredder residue. PB-05 employed a two-stage, back-mixed, slurry reactor system with an interstage V/L separator and an in-line fixed-bed hydrotreater. Coprocessing of waste plastics with Illinois No. 6 coal did not result in the improvement observed earlier with a subbituminous coal. In particular, decreases in light gas yield and hydrogen consumption were not observed with Illinois No. 6 coal as they were with Black Thunder Mine coal. The higher thermal severity during PB-05 is a possible reason for this discrepancy, plastics being more sensitive to temperatures (cracking) than either coal or heavy resid. The ASR material was poorer than MSW plastics in terms of increasing conversions and yields. HTI`s new dispersed catalyst formulation, containing phosphorus-promoted iron gel, was highly effective for the direct liquefaction of Illinois No. 6 coal under the reaction conditions employed; over 95% coal conversion was obtained, along with over 85% residuum conversion and over 73% distillate yields.

  15. Synthesis of model compounds for coal liquefaction research

    SciTech Connect

    Not Available

    1991-11-01

    Coal liquefaction investigations required the availability of model compounds for mechanistic investigations. Towards this end, IITRI was funded to develop an approach for the synthesis of one of the target compound. This study was carried out in several phases as outlined here. Initial synthetic investigations on obtaining 2-tetrolol was carried out using high pressure and temperature reduction with Raney nickel catalyst. The next step consisted in incorporation of a hydroxymethyelene group at the C-3 position. This was successfully carried out utilizing 2-tetrolol, formaldehyde, and calcium oxide. An alternate improved method was developed using 3-carboxyl-2-naphthol. This required less time, gave a cheer product in higher yield. Efforts at the introduction of a chloromethylene group only yielded polymeric material or starting material in spite of protection the phenolic group by various groups. They synthesis of 3, 5-dimethyl-6- bromobenzyl chloride was successfully carried out by performing the Blank reaction of 2, 4-dimethyl bromobenzene. The product was characterized by GC/MS. Purification was not possible, as it was a complex mixture. Efforts at converting it to the acetate followed by separation to was not feasible. Unlike in the case of 2- hydroxyteralol, hydroxymetylation by established procedure yielded only the starting materials. Commercially available 4-methoxy-1- maphthaldehyde was protected as the ethylene acetal. The Wittig reagent 3-chlorobenzyl phosphonium bromide was prepared and condensed with 4-methoxy-1-napthaldehyde successfully and proved that the overall synthetic approach was proceeding in the desired direction. All the necessary intermediates have been synthesized,and we have demonstrated using model compounds, that the synthetic objective can be attained.

  16. Coal liquefaction process streams characterization and evaluation. Quarterly technical progress report, October 1--December 31, 1992

    SciTech Connect

    Brandes, S.D.; Winschel, R.A.; Burke, F.P.; Robbins, G.A.

    1993-10-01

    The Research and Development Department of CONSOL Inc. is conducted a program to characterize process and product streams from direct coal liquefaction process development projects sponsored by the Department of Energy. In this program, CONSOL obtains samples from current process development activities in coal liquefaction and coal-oil coprocessing, and characterizes them using established analytical techniques. In addition, selected samples are characterized by other analytical techniques to evaluate their potential for aiding process development. These analyses and interpretation of the results in relation to process operations are provided by the subcontractor. Major topics reported in this thirteenth quarterly report are the following: (1) Analyses were performed on three coals and eleven process oils from HRI, Inc. process development unit Run 260--03, which was the first process development unit test of Black Thunder Mine subbituminous coal, significant operating problems were encountered, and sample properties are discussed in context to the operational problems; (2) a summary of the status of the Participants Program is given; (3) summaries of the final reports produced by the University of Chicago, the University of Utah, Iowa State University, and the University of Kentucky under the Participants Program, are presented.

  17. Effects of low-temperature catalytic pretreatments on coal structure and reactivity in liquefaction

    SciTech Connect

    Song, C.; Saini, A.K.; Wenzel, K.; Huang, L.; Hatcher, P.G.; Schobert, H.H.

    1993-04-01

    This work is a fundamental study of catalytic pretreatments as a potential preconversion step to low-severity liquefaction. The ultimate goal of this work is to provide the basis for the design of an improved liquefaction process and to facilitate our understanding of those processes that occur when coals are initially dissolved. The main objectives of this project are to study the effects of low-temperature pretreatments on coal structure and their impacts on the subsequent liquefaction. The effects of pretreatment temperatures, catalyst type, coal rank and influence of solvent will be examined. We have made significant progress in the following four aspects during this quarterly period: (1) influence of drying and oxidation of coal on the conversion and product distribution in catalytic liquefaction of Wyodak subbituminous coal using a dispersed catalyst; (2) spectroscopic characterization of dried and oxidized Wyodak coal and the insoluble residues from catalytic and thermal liquefaction; (3) the structural alteration of low-rank coal in low-severity liquefaction with the emphasis on the oxygen-containing functional groups; and (4) effects of solvents and catalyst dispersion methods in temperature-programmed and non-programmed liquefaction of three low-rank coals.

  18. Novel bimetallic dispersed catalysts for temperature-programmed coal liquefaction

    SciTech Connect

    Chunshan, Song; Kirby, S.; Schmidt, E.

    1995-12-31

    The objective of this project is to explore bimetallic dispersed catalysts for more efficient coal liquefaction. Coal liquefaction involves cleavage of methylene, dimethylene and ether bridges connecting various aromatic units and the reactions of various oxygen functional groups. This paper describes recent results on (1) hydrodeoxygenation of O-containing polycyclic model compounds using novel organometallic catalyst precursors; and (2) activity and selectivity of dispersed Fe catalysts from organometallic and inorganic precursors for hydrocracking of 4-(1-naphthylmethyl) bibenzyl. The results showed that some iron containing catalysts have higher activity in the sulfur-free form, contrary to conventional wisdom. Adding sulfur to Fe precursors with Cp-ligands decreased the activity of the resulting catalyst. This is in distinct contrast to the cases with iron pentacarbonyl and superfine Fe{sub 2}O{sub 3}, where S addition increased their catalytic activity substantially. A positive correlation between sulfur addition and increased activity can be seen, but a reversed trend between Fe cluster size and hydrocracking conversion could be observed, for carbonyl-type Fe precursors. It is apparent that the activity and selectivity of Fe catalysts for NMBB conversion depends strongly on both the type of ligand environment, the oxidation state and the number of intermetal bonds in the molecular precursor.

  19. Sequential low-temperature depolymerization and liquefaction of US coals

    SciTech Connect

    Shabtai, J.S.; Wiser, W.H.

    1987-07-01

    The Elkhorn (Kentucky) coal sample, referred below as EH(KY) coal, had the following ultimate analysis (MAF basis), in wt %: C, 85--36; H, 5.69; N, 1.75; Cl, 0.18; S, 0.72; 0 (diff) 6.30. H/C atomic ratio - 0.80; ash content (dry basis), 6.60 %. The sample showed a calorific value of 14,324 BTU/ib (dry basis). As indicated by its ultimate analysis and calorific value, the EH(Ky) coal was of somewhat higher rank as compared with the previously studied HVB coal sample from Burning Star (Illinois no. 6). The EH (Ky) coal was subjected to the previously developed stepwise depolyermization-liquefaction procedure summarized in Figure 1 [for details see J. Shabtai, T. Skulthai and I. Saito, Am. Chem. Soc. Div. Fuel Chem. Prepr., 31 (4), 15--23 (1986)]. The procedure consists essentially of the following sequential steps: (1) Intercalation of the coal sample with catalytic amounts (5--20 %) of FeCl[sub 3], followed by mild hydrotreatment (HT) of the coal-FeCl[sub 3] intercalate; (2) base-catalyzed depolymerization (BCD) of the product from step 1, under super-critical conditions; and (3) hydroprocessing (HPR) of the depolymerized product from the two preceding steps, using a sulfided 6Co8Mo catalyst. A systematic study was carried out with the purpose of determining the optimal range of processign conditions for EH (Ky) coal in each step of the above sequential procedure.

  20. Cooperative research in coal liquefaction. Final report, May 1, 1991--April 30, 1992

    SciTech Connect

    Huffman, G.P.

    1996-03-01

    Extensive research continued on catalysts based on novel anion-treated (mainly sulfated) oxides and oxyhydroxides of iron [Fe{sub x}O{sub y}/SO{sub 4}]. In addition, sulfated oxides of tin as well as molybdenum promoted iron oxides were used. Incorporation of small amounts of sulfate, molybdate, or tungstate anions by wet precipitation/impregnation methods was found to increase the surface acidic character of iron oxides; more importantly, it reduced the grain sizes significantly with corresponding increases in specific surface areas. These anion-treated iron and tin oxides were more active for direct coal liquefaction and coal-heavy oil coprocessing than their untreated counterparts. With these catalyst systems, higher conversion levels are obtained as compared to the soluble precursors of iron and molybdenum at the same catalyst metalloading (3500 ppm iron and 50 ppm molybdenum with respect to coal). Sulfated iron oxides and oxyhydroxides were equally active as coal liquefaction catalysts. The sulfate, molybdate, and tungstate anions were found to have similar promotional effects on the properties and activities of iron oxides. One step in the synthesis of anion-treated iron and tin oxides is precipitation as hydroxides using either urea or ammonium hydroxide. The catalysts prepared using urea as a precipitation agent were more reproducible than those using ammonium, hydroxide in terms of activities and properties. These catalysts/catalyst precursors were characterized by several techniques to determine their physical (size and structure related) and chemical (acidity) properties. Sulfated and molybdated iron oxides were found to have grain sizes as small as 10-20 nm. An attempt was made to correlate the physicochemical properties of these catalysts with their activity for coal liquefaction.

  1. Catalytic multi-stage liquefaction of coal. Eleventh quarterly progress report, April 1, 1995--June 30, 1995

    SciTech Connect

    Comolli, A.G.; Johanson, E.S.; Lee, L.K.

    1995-10-01

    This quarterly report covers the activities of Catalytic Multi-Stage Liquefaction of Coal during the Period April 1 - June 30, 1995, at Hydrocarbon Technologies, Inc. in Lawrenceville, New Jersey. This DOE Contract Period was from December 8, 1992 to December 7, 1994 and has been extended to September 30, 1995. The overall objective of this program is to produce liquid fuels from coal by direct liquefaction at a cost that is competitive with conventional fuels. Specifically, this continuous bench-scale program contains provisions to examine new ideas in areas such as: low temperature pretreatments, more effective catalysts, on-line hydrotreating, new coal feedstocks, other hydrogen sources, more concentrated coal feeds and other highly responsive process improvements while assessing the design and economics of the bench-scale results. This quarterly report covers work on Laboratory Scale Studies, Continuous Bench-Scale Operations, Technical Assessment and Project Management.

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

    SciTech Connect

    Klein, M.T.; Calkins, W.H.; Huang, H.; Wang, S.; Campbell, D.

    1998-03-01

    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.

  3. Effects of low-temperature catalytic pretreatments on coal structure and reactivity in liquefaction

    SciTech Connect

    Song, C.; Saini, A.K.; Huang, L.; Wenzel, K.; Hou, L.; Hatcher, P.G.; Schobert, H.H.

    1992-08-01

    Low-temperature catalytic pretreatment is a promising approach to the development of an improved liquefaction process- This work is a fundamental study on effects of pretreatments on coal structure and reactivity in liquefaction. The main objectives of this project are to study the coal structural changes induced by low-temperature catalytic and thermal pretreatments by using spectroscopic techniques; and to clarify the pretreatment-induced changes in reactivity or convertibility of coals in the subsequent liquefaction. This report describes the recent progress of our work. Substantial progress has been made in the spectroscopic characterization of structure and pretreatment-liquefaction reactions of a Montana subbituminous Coal (DECS-9), and thermochemical analysis of three mw and reacted bituminous coals. Temperature programmed liquefaction has been performed on three low-rank coals both in the presence and absence of dispersed molybdenum sulfide catalyst. We also performed a detailed study of the effects of mild thermal pretreatment -- drying in air and in vacuum -- on thermal and catalytic liquefaction of a Wyodak subbituminous coal. Important information on structure and structure transformation during thermal pretreatment and liquefaction reactions of low-rank coals has been derived by applying solid-state CPMAS [sup 13]C NMR and flash pyrolysis-GC-MS (Py-GC-MS) for characterization of the macromolecular network of a Montana subbituminous coal and its residues from temperature-programmed and nonprogrammed liquefaction (TPL and N-PL) at final temperatures ranging from 300 to 425[degree]C in H-donor and non-donor solvents. The results revealed that this coal contains significant quantities of oxygen-bearing structures, corresponding to about 18 O-bound C per 100 C atoms and one O-bound C per every 5 to 6 aromatic C.

  4. Catalytic multi-stage liquefaction of coal. Tenth quarterly report, January 1--March 31, 1995

    SciTech Connect

    Comolli, A.G.; Johanson, E.S.; Lee, L.K.; Pradhan, V.R.; Stalzer, R.H.

    1995-05-01

    The overall objective of this program is to produce liquid fuels from coal by direct liquefaction at a cost that is competitive with conventional fuels. Specifically, this continuous bench-scale program contains provisions to examine new ideas in areas such as: low temperature pretreatments, more effective catalysts, on-line hydrotreating, new coal feedstocks, other hydrogen sources, more concentrated coal feeds and other highly responsive process improvements while assessing the design and economics of the bench-scale results. This report describes the following: (1) laboratory support for bench run CMSL-09, (2) the laboratory-scale efforts for development of suitable catalysts for hydrocracking/depolymerization of waste plastics, (3) analysis of TBP (true boiling point) fractions of distillates from CMSL-08, and (4) objectives and run-plan for bench run CMSL-09.

  5. Activity testing of fine-particle size, iron catalysts for coal liquefaction

    SciTech Connect

    Stohl, F.V.; Diegert, K.V.; Gugliotta, T.P.

    1993-10-01

    The use of fine-particle size (< 40 nm) unsupported catalysts in direct coal liquefaction may result in improved economics due to possible enhanced yields of desired products, the potential for decreasing reaction severity, and the possibility of using less catalyst. Sandia has developed a standard testing procedure for evaluating and comparing the fine-particle catalysts. The test procedure uses phenanthrene as the reaction solvent, the DECS-17 Blind Canyon Coal, and a statistical experimental design to enable evaluation of the catalysts over ranges of temperature (350 to 400{degrees}C), time (20 to 60 minutes), and catalyst loading (0 to 1 wt % on a dmmf coal basis). Product analyses include tetrahydrofuran (THF) conversion, heptane conversion, solvent recovery, and gas analyses. Phenanthrene as the solvent in the testing procedure yielded significant differences between thermal and catalytic reactions, whereas using a good hydrogen donor such as 9,10-dihydrophenanthrene (DHP) showed no catalytic effects.

  6. Coal liquefaction laboratory studies. Volume 2. Two-stage variations: subbituminous coal

    SciTech Connect

    Bynum, R.; Carver, J.M.; Gir, S.; Paranjape, A.S.; Rhodes, D.E.

    1985-07-01

    Laboratory studies were made to evaluate the technical feasibility of new process concepts and advanced coal liquefaction processes at the bench-scale level to produce environmentally-acceptable fuel and other useable by-products. This report summarizes the results of batch reactor studies completed during the period of January through July 1983. The laboratory studies covered several wide ranging topics including temperature-staged coal dissolving, co-processing of coal and petroleum, disposable catalysts and heterocyclic solvents. Good coal conversions and distillate yields were obtained from Wyoming subbituminous coal by using temperature-staged dissolving in the presence of iron oxide as a disposable catalyst. Similarly, petroleum-based asphaltenes were successfully co-processed with subbituminous coal in the presence of iron oxide with high coal conversions. Use of heterocyclic compounds as a component of liquefaction solvent resulted in high losses of these compounds to products rather than remain with the recycle solvent. During these laboratory studies, a simple reproducible batch test was developed to provide fast evaluation and screening of different catalysts for hydrotreatment of different resids. 33 refs., 8 figs., 44 tabs.

  7. Advanced liquefaction using coal swelling and catalyst dispersion techniques. Quarterly technical progress report, January--March 1993

    SciTech Connect

    Curtis, C.W.; Gutterman, C.; Chander, S.

    1993-09-01

    The overall objective of this project is 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 integrates coal selection, pretreatment, coal swelling with catalyst impregnation, liquefaction, product recovery with characterization, alternate bottoms processing, and carrying out a technical assessment including an economic evaluation. The primary coal of this program, Black Thunder subbituminous coal, can be effectively beneficiated to about 4 wt% ash using aqueous sulfurous acid pretreatment. This treated coal can be further beneficiated to about 2 wt% ash using commercially available procedures. All three coals used in this study (Black Thunder, Burning Star bituminous, and Martin Lake lignite) are effectively swelled by a number of solvents. The most effective solvents are those having hetero-functionality. In addition, a synergistic effect has been demonstrated, in which solvent blends are more effective for coal swelling than the pure solvents alone. Therefore, it will be necessary to use only low levels of swelling agents and yet promote the impregnation of catalyst precursors. The rate of the impregnation of catalyst precursors into swollen coal increases greatly as the effectiveness of the solvent to swell the coal increases.

  8. Characteristics of process oils from HTI coal/plastics co-liquefaction runs

    SciTech Connect

    Robbins, G.A.; Brandes, S.D.; Winschel, R.A.

    1995-12-31

    The objective of this project is to provide timely analytical support to DOE`s liquefaction development effort. Specific objectives of the work reported here are presented. During a few operating periods of Run POC-2, HTI co-liquefied mixed plastics with coal, and tire rubber with coal. Although steady-state operation was not achieved during these brief tests periods, the results indicated that a liquefaction plant could operate with these waste materials as feedstocks. CONSOL analyzed 65 process stream samples from coal-only and coal/waste portions of the run. Some results obtained from characterization of samples from Run POC-2 coal/plastics operation are presented.

  9. Automated apparatus for solvent separation of a coal liquefaction product stream

    DOEpatents

    Schweighardt, Frank K.

    1985-01-01

    An automated apparatus for the solvent separation of a coal liquefaction product stream that operates continuously and unattended and eliminates potential errors resulting from subjectivity and the aging of the sample during analysis. In use of the apparatus, metered amounts of one or more solvents are passed sequentially through a filter containing the sample under the direction of a microprocessor control means. The mixture in the filter is agitated by means of ultrasonic cavitation for a timed period and the filtrate is collected. The filtrate of each solvent extraction is collected individually and the residue on the filter element is collected to complete the extraction process.

  10. Mechanism of hydrogen incorporation in coal liquefaction. Progress report as of June 31, 1994

    SciTech Connect

    Not Available

    1994-08-01

    The authors are continuing work on the reaction of D{sub 2} with organic compounds relevant to coal liquefaction. The thermal and silica-catalyzed hydrogenation reactions of unsaturated organics (using deuterium) have been studied.

  11. Applied research and evaluation of process concepts for liquefaction and gasification of western coals. Final report

    SciTech Connect

    Wiser, W. H.

    1980-09-01

    Fourteen sections, including five subsections, of the final report covering work done between June 1, 1975 to July 31, 1980 on research programs in coal gasification and liquefaction have been entered individually into EDB and ERA. (LTN)

  12. Advanced direct liquefaction concepts for PETC generic units. Final report, Phase I

    SciTech Connect

    1995-03-01

    The Advanced Concepts for Direct Coal Liquefaction program was initiated by the Department of Energy in 1991 to develop technologies that could significantly reduce the cost of producing liquid fuels by the direct liquefaction of coal. The advanced 2-stage liquefaction technology that was developed at Wilsonville over the past 10 years has contributed significantly toward decreasing the cost of producing liquids from coal to about $33/bbl. It remains, however, the objective of DOE to further reduce this cost to a level more competitive with petroleum based products. This project, among others, was initiated to investigate various alternative approaches to develop technologies that might ultimately lead to a 25 % reduction in cost of product. In this project a number of novel concepts were investigated, either individually or in a coupled configuration that had the potential to contribute toward meeting the DOE goal. The concepts included mature technologies or ones closely related to them, such as coal cleaning by oil agglomeration, fluid coking and distillate hydrotreating and dewaxing. Other approaches that were either embryonic or less developed were chemical pretreatment of coal to remove oxygen, and dispersed catalyst development for application in the 2-stage liquefaction process. This report presents the results of this project. It is arranged in four sections which were prepared by participating organizations responsible for that phase of the project. A summary of the overall project and the principal results are given in this section. First, however, an overview of the process economics and the process concepts that were developed during the course of this program is presented.

  13. Corrosion and stress corrosion cracking in coal liquefaction processes

    SciTech Connect

    Baylor, V. B.; Keiser, J. R.

    1980-01-01

    The liquefaction of coal to produce clean-burning synthetic fuels has been demonstrated at the pilot plant level. However, some significant materials problems must be solved before scale-up to commercial levels of production can be completed. Failures due to inadequate materials performance have been reported in many plant areas: in particular, stress corrosion cracking has been found in austenitic stainless steels in the reaction and separation areas and several corrosion has been observed in fractionation components. In order to screen candidate materials of construction, racks of U-bend specimens in welded and as-wrought conditions and unstressed surveillance coupons were exposed in pilot plant vessels and evaluated. Failed components were analyzed on-site and by subsequent laboratory work. Laboratory tests were also performed. From these studies alloys have been identified that are suitable for critical plant locations. 19 figures, 7 tables.

  14. Novel technologies for the production of ultrafine coal liquefaction catalysts

    SciTech Connect

    Matson, D.W.; Linehan, J.C.; Fulton, J.L.; Bean, R.M.

    1991-10-01

    Unusual materials processing technologies offer the potential for forming ultrafine iron-bearing particles suitable for coal liquefaction catalysis. Two such technologies currently under development at the Pacific Northwest Laboratory are the rapid expansion of supercritical fluid solutions (RESS) process and the precipitation of ultrafine particles in reverse micelle solutions. The RESS process involves expansion of dilute solutions through a small orifice from pressures and temperatures at which they exist as supercritical fluids, to ambient or near ambient conditions such that the post-expansion solvent exists solely in the gaseous phase. The abrupt drop in solvent density and the resulting solute particle nucleation and growth which occur during a RESS expansion promote formation of an ultrafine aerosol consisting of nanometer to micrometer scale solid solute particles. Precipitation of iron sulfides and iron oxides in reverse micelle systems as an alternative route to nanometer scale particle formation is also discussed.

  15. A CHARACTERIZATION AND EVALUATION OF COAL LIQUEFACTION PROCESS STREAMS

    SciTech Connect

    G.A. Robbins; S.D. Brandes; D.J. Pazuchanics; D.G. Nichols; R.A. Winschel

    1998-12-01

    This is the Technical Progress Report for the fifteenth quarter of activities under DOE Contract No. DE-AC22-94PC93054. It covers the period January 1 through March 31, 1998. Described in this report are the following activities: (1) CONSOL characterized 41 process stream samples obtained from HTI Run PB-01 (227-90), in which Black Thunder Mine coal, Hondo VTB resid, municipal solid waste (MSW) plastics, and virgin plastics were co-liquefaction feedstocks with all-dispersed Fe and Mo catalysts. (2) A request was made for samples from the Nippon Coal Oil NEDOL pilot plant in Kashima, Japan. (3) Phenols were extracted from two samples of separator overhead oil from HTI Run PB-03 Periods 10A and 10B. The phenols were converted to ethylphenyl ethers, and the ethers were distilled to produce a sample within the diesel fuel boiling range. The ethers were mixed with diesel fuel to make 1%, 5%, 10%, and 20% solutions. The four mixtures and a control sample (0% ether) were tested for diesel fuel properties by Intertek Testing Services, Caleb Brett. (4) Computational studies related to the University of Delaware's resid conversion model were continued on the Hewlett Packard Apollo HP-735 RISC workstation at CONSOL R and D. The Structure Optimization Program and the Structure Once-Through Program were used to generate physicochemical properties and structure models for the 15 coal resid samples which have been under study.

  16. Coal-derived promoters for the liquefaction of Illinois coal. Technical report, March 1--May 31, 1992

    SciTech Connect

    Carty, R.H.; Knight, R.A.

    1992-10-01

    The objective of this program is to investigate the use of liquids derived from coal either by mild gasification (MG) or supercritical extraction (SCE) to promote direct liquefaction of Illinois coal. Some organic heteroatomic compounds have been found to enhance liquefaction reactions. The approach taken in this two-year program is to use recently developed molecular probe techniques to assess the reactivity of three coal-derived liquids with respect to (A) H transfer rate, (B) C-C bond cleavage rate, (C) free radical flux, and (D) hydrocracking activity. With the IFFR liquid, the H transfer rate showed a mean increase of 21%, C-C bond cleavage selectivity increased by 34%, free radical flux showed a mean increase of 107%, and overall mean hydrocracking activity increased by 269%. For the ST/FBR liquid, H transfer rate increased 7%, C-C bond cleavage selectivity increased 27%, free radical flux increased 101%, and data indicated a 227% increase in hydrocracking activity. During the current quarter, the SCE liquid was characterized and tested. The H transfer rate did not increase, the mean free radical flux increased by 18%, and the hydrocracking activity showed a dramatic increase of 359%, which is higher than either the IFFR or ST/FBR liquids. The assessment of C-C bond cleavage with SCE is not yet completed. The SCE analysis showed much lower levels of phenols, cresols, and naphthalenes than the IFFR and ST/FBR liquids.

  17. Assessment of Long-Term Research Needs for Coal-Liquefaction Technologies

    SciTech Connect

    Penner, S.S.

    1980-03-01

    The Fossil Energy Research Working Group (FERWG), at the request of J.M. Deutch (Under Secretary of DOE), E. Frieman (Director, Office of Energy Research) and G. Fumich, Jr. (Assistant Secretary for Fossil Fuels), has studied and reviewed currently funded coal-liquefaction technologies. These studies were performed in order to provide an independent assessment of critical research areas that affect the long-term development of coal-liquefaction technologies. This report summarizes the findings and research recommendations of FERWG.

  18. Fine particle clay catalysts for coal liquefaction. Quarterly technical progress report, November 9, 1992--February 8, 1993

    SciTech Connect

    Olson, E.S.

    1995-10-01

    The mixed iron/alumina pillared clay catalysts and clay-supported iron catalysts have been shown in previous reports of this project to significantly improve yields of heptane-soluble products obtained in the liquefaction of both as received and acid-exchanged Wyodak subbituminous coal and Blind Canyon bituminous coal. In this quarter, the soluble product (LSW) obtained from the noncatalytic low-severity liquefaction of Wyodak coal was used as a feed to determine the activity of iron based catalysts for the hydrogenation and depolymerization steps. Comparison data for liquefaction of the soluble LSW with other catalysts were desired, and these data were obtained for a dispersed form of iron sulfide, prepared via iron hydroxyoxide (PETC method). The iron oxyhydroxide catalyst was directly precipitated on LSW product using either water or ethanol as the solvent. An insight into the functioning of the mixed iron/alumina pillared clay in coal liquefaction was investigated by preparing and studying an iron oxoaluminate structure. An investigation of new methods for the production of tetralin soluble iron oxometallate catalysts and the determination of their catalytic activities was continued in this quarter. The hydrogenation activity of iron oxoaluminate was investigated using pyrene and 1-methylnaphthalene as the test compounds, and results were compared with thermal reactions. In order to determine the loss of activity, recovered catalyst was recycled a second time for the hydrotreating of pyrene. Reaction of 1-methylnaphthalene with iron oxoaluminate also gave very high conversion to 1- and 5-methyltetralins and small amount of 2- and 6-methyltetralins. Liquefaction of Wyodak subbituminous and Blind Canyon bituminous coal was investigated using an in situ sulfided soluble iron oxoaluminate catalyst.

  19. Type II preliminary pilot-plant evaluation of a coal-liquefaction residue - water slurry using vaccum-tower bottoms from the H-Coal liquefaction process

    SciTech Connect

    Wu, C.M.; Robin, A.M.

    1982-09-01

    About 6.7 tons of vacuum tower bottoms (residue) which were obtained during the liquefaction of Illinois No. 6 coal from the H-Coal liquefaction process pilot plant at Catlettsburg, Kentucky were successfully gasified at Texaco's Montebello Research Laboratory. The single 9.5-hour run with H-Coal liquefaction residue-water slurry was completed at 750 to 760 psig gasifier pressure. The run consisted of two test periods, each at a different gasifier temperature. Over 99.6 percent conversion of carbon in the feed to syngas was achieved yielding 32.9 to 33.7 standard cubic feet of dry syngas per pound of residue charged. The oxygen requirement was about 1.0 pound of oxygen per pound of residue. The dry syngas contained 78.5 to 79.7 (vol.) percent carbon monoxide plus hydrogen.

  20. Coal liquefaction process streams characterization and evaluation. Quarterly technical progress report, January 1--March 31, 1992

    SciTech Connect

    Robbins, G.A.; Brandes, S.D.; Winschel, R.A.; Burke, F.P.

    1992-08-01

    This is the tenth Quarterly Technical Progress Report under DOE Contract DE-AC22-89PC89883. Process oils from Wilsonville Run 262 were analyzed to provide information on process performance. Run 262 was operated from July 10 through September 30, 1991, in the thermal/catalytic Close-Coupled Integrated Two-Stage Liquefaction (CC-ITSL) configuration with ash recycle. The feed coal was Black Thunder Mine subbituminous coal. The high/low temperature sequence was used. Each reactor was operated at 50% of the available reactor volume. The interstage separator was in use throughout the run. The second-stage reactor was charged with aged Criterion 324 catalyst (Ni/Mo on 1/16 inch alumina extrudate support). Slurry catalysts and sulfiding agent were fed to the first-stage reactor. Molyvan L is an organometallic compound which contains 8.1% Mo, and is commercially available as an oil-soluble lubricant additive. It was used in Run 262 as a dispersed hydrogenation catalyst precursor, primarily to alleviate deposition problems which plagued past runs with Black Thunder coal. One test was made with little supported catalyst in the second stage. The role of phenolic groups in donor solvent properties was examined. In this study, four samples from direct liquefaction process oils were subjected to O-methylation of the phenolic groups, followed by chemical analysis and solvent quality testing.

  1. Coal liquefaction process utilizing coal/CO.sub.2 slurry feedstream

    DOEpatents

    Comolli, Alfred G.; McLean, Joseph B.

    1989-01-01

    A coal hydrogenation and liquefaction process in which particulate coal feed is pressurized to an intermediate pressure of at least 500 psig and slurried with CO.sub.2 liquid to provide a flowable coal/CO.sub.2 slurry feedstream, which is further pressurized to at least 1000 psig and fed into a catalytic reactor. The coal particle size is 50-375 mesh (U.S. Sieve Series) and provides 50-80 W % coal in the coal/CO.sub.2 slurry feedstream. Catalytic reaction conditions are maintained at 650.degree.-850.degree. F. temperature, 1000-4000 psig hydrogen partial pressure and coal feed rate of 10-100 lb coal/hr ft.sup.3 reactor volume to produce hydrocarbon gas and liquid products. The hydrogen and CO.sub.2 are recovered from the reactor effluent gaseous fraction, hydrogen is recycled to the catalytic reactor, and CO.sub.2 is liquefied and recycled to the coal slurrying step. If desired, two catalytic reaction stages close coupled together in series relation can be used. The process advantageously minimizes the recycle and processing of excess hydrocarbon liquid previously needed for slurrying the coal feed to the reactor(s).

  2. ADVANCED DIRECT LIQUEFACTION CONCEPTS FOR PETC GENERIC UNITS

    SciTech Connect

    Adam J. Berkovich

    2000-02-01

    The results of Laboratory and Bench-Scale experiments and supporting technical and economic assessments conducted under DOE Contract No. DE-AC22-91PC91040 is reported for the period July 1, 1998 to September 30, 1998. This contract is with the University of kentucky Research Foundation, which supports work with the University of Kentucky Center for Applied Energy Researc, CONSOL, Inc., LDP Associates, and Hydrocarbon Technologies, Inc. This work involves the introduction into the basic two-stage liquefaction process several novel concepts, which include dispersed lower-cost catalysts, coal cleaning by oil agglomeration, and distillate hydrotreating and dewaxing. This project has been modified to include an investigation into the production of value added materials from coal using liquefaction based technologies.

  3. Catalytic multi-stage liquefaction of coal twelth quarterly report for the period 1 July 1995--30 September 1995

    SciTech Connect

    Comolli, A.G.; Johanson, E.S.; Lee, L.K.; Pradhan, V.R.; Stalzer, R.H.

    1995-12-01

    The overall objective of this program is to produce liquid fuels from coal by direct liquefaction at a cost that is competitive with conventional fuels. Specifically, this continuous bench-scale program contains provisions to examine new ideas in areas such as: low temperature pretreatments, more effective catalysts, on-line hydrotreating, new coal feedstocks, other hydrogen sources, more concentrated coal feeds and other highly responsive process improvements while assessing the design and economics of the bench- scale results. This quarterly report covers work on Laboratory Scale Studies, Continuous Bench-Scale Operations, Technical Assessment and Project Management.

  4. Coal liquefaction and gas conversion: Proceedings. Volume 2

    SciTech Connect

    Not Available

    1993-12-31

    Volume II contains papers presented at the following sessions: Indirect Liquefaction (oxygenated fuels); and Indirect Liquefaction (Fischer-Tropsch technology). Selected papers have been processed separately for inclusion in the Energy Science and Technology Database.

  5. Some general laws of the thermolysis of coal structure simulating substances and their application of liquefaction technology

    SciTech Connect

    Kalechits, I.V.; Korobkov, V.Yu.; Golovin, G.S.

    1994-12-31

    During coal liquefaction, the transformation of the organic matter in coal beginds with the destruction into high molecular weight fragments which further break up under optimal conditions. This paper describes the thermodynamics associated with the thermolysis of aryls in phenylaryl and benzyl aryl ethers, and dibenzyl. Results are related to, or compared to, coal liquefaction conditions.

  6. Cooperative research in coal liquefaction infratechnology and generic technology development: Quarterly report, July 1-October 1, 1987. [Kentucky coal deposits

    SciTech Connect

    Huffman, G.P.; Sendlein, L.V.A.

    1987-01-01

    Research programs in coal liquefaction continued in the following areas: (1) catalytic coal liquefaction using Mo catalysts; (2) coprocessing experiments, using Maya topper long resid as a solvent for Illinois No. 6 coal using a variety of both unimodal and bimodal catalysts. The effect of agitation rate on conversion in a horizontally aligned tubing bond experiment was investigated; (3) the effect of tetrabutyltin and FeSO/sub 4/ . 7H/sub 2/O catalysts on coprocessing. A mathematical model was used to determine critical coprocessing rate constants; (4) a study of the bond cleavage reactions of benzl phenyl ethers was completed. Similar bond cleavages may be induced in coal and lead to liquid products under low severity conditions. EPR studies of Cr(V) model compounds established an unusual lineshape. Solvent extraction using N-methyl-2-pyrrolidone on a high resinite coal from Utah. New NMP experimets are in progress on oil shales and tar sands. New experimental apparatus has been devised for investigating the kinetics of the extraction process; (5) collection and analysis of the eastern Kentucky coals was completed. Chemical and petrographic analyses were placed in the KECL coal data base; (6) liquefaction screening of the eastern Kentucky coals was completed. Liquefaction data is being correlated with the coal properties; (7) a new /sup 13/C NMR technique, variable angle sample spinning (VASS), show great promise for determining the average cluster size in coal. Sink/float methods are being developed to obtain gram quantities of maceral enriched (> 90%) specimens on which liquefaction studies can be made. Pyrolysis and mass spectrometry studies are being made on raw Elkhorn coal; (8) biological desulfurization studies emphasized experiments with Sulfolobus brierleyi. The growth of Sulfolobus solfataricus on casamino acids and yeast extract was investigated; (9) the CFFLS computer network/liquefaction database became operational. 4 refs., 13 figs., 18 tabs.

  7. The permeation by liquefied coal of gloves used in coal liquefaction pilot plants

    SciTech Connect

    Bennett, R.D.

    1983-06-01

    The protective capabilities of PVC, natural rubber and milled nitrile rubber gloves currently used in coal liquefaction pilot plants were assessed, and the effectiveness of a laundering method was evaluated. The breakthrough times and cumulative permeation for exposure to toluene and to liquefied coal were determined by measurement of radiolabelled phenol tracer in the aqueous receiving medium. Breakthrough times agreed with the findings of other studies on exposure to liquefied coal, the nitrile laboratory glove resisted breakthrough the longest (12-14 h), although it was the thinnest material tested. Breakthrough times for the other gloves ranged from 2.75 to 6.5 h. Normalised for thickness, both PVC materials tested were more resistant to breakthrough than rubber. The laundering method did not completely decontaminate samples of PVC glove material pre-exposed to liquefied coal for 24 h under laboratory conditions.

  8. Effects of low-temperature catalytic pretreatments on coal structure and reactivity in liquefaction

    SciTech Connect

    Song, C.; Saini, A.; Huang, L.; Wenzel, K.; Hatcher, P.G.; Schobert, H.H.

    1992-01-01

    Low-temperature catalytic pretreatment is a promising approach to the development of an improved liquefaction process. This work is a fundamental study on effects of pretreatments on coal structure and reactivity in liquefaction. The main objectives of this project are to study the coal structural changes induced by low-temperature catalytic and thermal pretreatments by using spectroscopic techniques; and to clarify the pretreatment-induced changes in reactivity or convertibility of coals in the subsequent liquefaction. This report describes the progress of our work during the first quarterly period. Substantial progress has been made in the spectroscopic characterization of fresh and THF-extracted samples of two subbituminous coals and fresh samples of three bituminous coals using cross-polarization magic angle spinning (CPMAS) solid state {sup 13}C NMR and pyrolysis-GC-MS techniques. CPMAS {sup 13}C NMR and pyrolysis-GC-MS provided important information on carbon distribution/functionality and molecular components/structural units, respectively, for these coal samples. Pyrolysis-GC-MS revealed that there are remarkable structural differences in structural units between the subbituminous coals and the bituminous coals. Furthermore, significant progress has been made in the pretreatments and spectroscopic characterization of catalytically and thermally pretreated as well as physically treated Wyodak subbituminous coal, and temperature-staged and temperature-programmed thermal and catalytic liquefaction of a Montana subbituminous coal.

  9. Phase equilibrium in coal liquefaction processes. Final report

    SciTech Connect

    Chao, K.C.

    1984-08-01

    Gas-liquid equilibrium data have been determined in simulation of coal liquefaction process conditions in mixtures of light gases + heavy hydrocarbons to add to the accumulated data previously reported in EPRI AP-1593. The mixture systems newly investigated are: methane + 9,10 dihydrophenanthrene; hydrogen + methane + 1-methylnaphthalene; hydrogen + carbon dioxide + tetralin; hydrogen + carbon dioxide + 1-methynaphthalene; hydrogen + carbon dioxide + quinoline; nitrogen + tetralin, + n-hexadecane, + 1-methylnaphthalene, + quinoline, and + m-cresol. Correlations for the solubilities of methane and carbon dioxide have been developed from the data based on the use of solubility parameter. The solubility of hydrogen was correlated in EPRI AP-1593. Two equations of state are developed for the description of both the gas solubility and the vaporization of the heavy oil. The Chain-of-Rotators (COR) equation of state explicitly accounts for the rotational molecular motion contribution to the pressure of a fluid. The Cubic-Chain-of-Rotators (CCOR) equation is obtained upon simplifying the COR equation. Interaction constants in the CCOR equation have been determined for the light gases with the heavy hydrocarbons based on data from this project, and the constants are correlated. Equilibrium flash vaporization has been experimentally determined for three coal liquids and for their mixtures with hydrogen. The data are correlated with the CCOR equation of state. 74 figures, 46 tables.

  10. Stress-corrosion cracking studies in coal-liquefaction systems

    SciTech Connect

    Baylor, V.B.; Keiser, J.R.

    1981-01-01

    Coal liquefaction plants with 6000 ton/d capacity are currently being planned by DOE as a step toward commercial production of synthetic fossil fuels. These plants will demonstrate the large-scale viability of the Solvent Refined Coal (SRC) process, which has been used since 1974 in two operating pilot plants: a 50-ton/d unit at Fort Lewis, Washington, and a 6-ton/d plant in Wilsonville, Alabama. Experience in these plants has shown that austenitic stainless steels are susceptible to stress corrosion cracking associated with residual stresses from cold working or welding. The corrodants responsible for the cracking have not yet been positively identified but are suspected to include polythionic acids and chlorides. To screen candidate materials of construction for resistance to stress corrosion cracking, racks of stressed U-bend specimens in welded and as-wrought conditions have been exposed at the Wilsonville and Fort Lewis SRC pilot plants. These studies have identified alloys that are suitable for critical plant applications.

  11. A Characterization and Evaluation of Coal Liquefaction Process Streams

    SciTech Connect

    Robbins, G.A.; Brandes, S.D.; Winschel, R.A.

    1997-03-31

    This is the Technical Progress Report for the tenth quarter of activities under DOE Contract No. DE-AC22-94PC93054. It covers the period October 1 through December 31, 1996. Described in this report are the following activities: (1) CONSOL characterized two HTI coal/petroleum coprocessing samples for Ni and V concentrations, as requested by DOE. The results are reported in Appendix 1. (2) CONSOL began work to evaluate the potential for producing alkylphenyl ethers, and specifically ethylphenyl ethers, from coal liquefaction phenols. The work includes a literature review and experimentation. The status of this ongoing work is described in this report. (3) A set of samples was requested from HTI Run ALC-2 (Appendix 2). (4) The University of Delaware is conducting resid reactivity tests and is developing a kinetic mechanistic model of resid reactivity. A summary of Delaware`s progress is appended to this report (Appendix 3). (5) A paper was submitted for presentation at the 213th National Meeting of the American Chemical Society, April 13-17, 1997, in San Francisco, CA, (Appendix 4).

  12. Evaluation of coal minerals and metal residues as coal-liquefaction catalysts

    SciTech Connect

    1982-02-01

    Under DOE Contract No. DE-AC22-79ET14806, Air Products and Chemicals, Inc., subcontracted Auburn University Coal Conversion Laboratory to perform exploratory studies on the use of minerals and by-product metallic wastes in coal liquefaction. Under this program Auburn University conducted an extensive screening program on numerous materials from which the more active or interesting ones were further investigated in the continuous process development units (PDU) at Air Products. In Volume 1 of the final report a number of the results from those tests are summarized for comparison with the PDU results. Because of the very extensive and detailed work performed at Auburn University, a portion of that work is not included in Volume 1. Therefore, in order to fulfill the requirements of the contract with DOE, a compilation of the work performed by Auburn University is submitted in Volume 2. The information from the Auburn University work was compiled from a sequence of monthly reports submitted to air Products and Chemicals, Inc., during the course of the program. Because of the very large numbers of screening runs conducted at Auburn, the overlap between these reports is minimal. This work presents in some detail the various stages of development of screening procedures and analytical methods that were developed. The reader should also find them extremely informative as to the generation of ideas that developed during this program. The work reported in this volume went beyond simple screening runs. Extensive exploratory studies as well as basic studies on the behavior of reactants and catalysts were performed. These results from the basic and exploratory studies impacted on the overall direction of this program.

  13. High dispersed catalysts for coal liquefaction. Quarterly report No. 7, February 23, 1993--May 22, 1993

    SciTech Connect

    Hirschon, A.S.; Wilson, R.B.

    1993-08-19

    The objectives of this project are to study the effect of pretreatment methods on the two-stage liquefaction process. In particular, the effects of dispersed catalysts and carbon monoxide atmospheres on a coal liquefaction process. The project is divided into three technical tasks. Task 1 involves the analyses of the liquefaction products derived from liquefaction experiments using the catalysts Fe(CO){sub 5} and the sulfated iron catalyst, Fe{sub 2}O{sub 3}{center_dot}SO{sub 4}. We also analyzed the products derived from treating the recycle vehicle under coal liquefaction conditions with no coal or catalyst present, and found that the toluene and THF fractions had low H/C ratios. No CO or CO{sub 2} gases were detected after reaction, although considerable amount of methane gas was produced, suggesting that during the liquefaction runs the carbon oxides are produced only from the coal, as expected, but that methane gas is produced both from the recycle solvent and the coal. We now have more information about the recycle solvent from Wilsonville, who report that the residue was 63%, composed of 45% resid and 18% insoluble inorganic (CI), and a distilable portion of 37% (1050{degrees}F). During this quarter we compared coal conversions using Fe(CO){sub 5} with CO and H{sub 2}/CO atmospheres and determined the effect of using sulfated iron (Fe{sub 2}O{sub 3}{center_dot}SO{sub 4}) as a conversion catalyst. Also, the coal liquefaction recycle vehicle was subjected to coal product distribution. We found that the Fe(CO){sub 5} under a pure hydrogen atmosphere gave better conversions than under a CO/H{sub 2} atmosphere in terms of oils and asphaltenes but was equal in terms of overall conversion into soluble fractions.

  14. Reactivity of heteroatom-containing organics during liquefaction of subbituminous coal: Quarterly technical progress report, March 15, 1988-June 15, 1988

    SciTech Connect

    Aulich, T.R.; Knudson, C.L.; Hawthorne, S.B.

    1988-01-01

    Deuteration of AO4 liquefaction solvent to an isotopic purity of approximately 99% was accomplished using a teflon-lined Parr bomb reactor. Tubing bomb liquefaction tests were performed using two sets of reaction conditions including coal and AO4, and coal and deuterated AO4. The THF insolubles to be used in testing the stability of the deuterated AO4 under liquefaction conditions were extracted using a Soxhlet apparatus and methylene chloride solvent. A system enabling product slurry distillation directly from the tubing bomb following completion of the liquefaction reaction was designed, constructed, and utilized to recover and quantitate volatile fractions of product slurries. The AO4 solvent was also distilled using the same equipment and procedure. Weighed amounts of eight deuterium-labeled species were added to weighed amounts of both labeled and non-labeled AO4 in preparation for the four remaining tubing bomb tests. 3 figs.

  15. Development of significantly improved catalysts for coal liquefaction and upgrading of coal extracts

    SciTech Connect

    Sinha, V.T.; Kutzenco, P.D.; Preston, W.J.; Brinen, J.S.; Graham, S.W.; Butensky, M.; Muchnick, T.L.; Hyman, D.

    1982-01-01

    During 1979-80, a new generation of very active, long-lived catlaysts for hydrotrating was discovered at the Stamford Research Laboratories of the American Cyanamid Company. The catalysts are based on a unique substrate prepared in bead form from a rehydratable alumina. Their spherical shape, crush strength, and abrasion resistance seem ideally suited for the ebullated bed reactors used in the H-COAL process developed by Hydrocarbon Research, Inc. (HRI). The beads have internal pore structures that are controllable over a wider range than conventional alumina supports, leading to active catalysts that are resistant to poisoning. In September, 1981, the Department of Energy granted a 3-year contract to the American Cyanamid Company for the development of significantly improved catalysts for coal liquefaction anf for upgrading coal extracts, particularly in reactors used in the H-COAL process. Catalysts will first be screened in a batch reactor to identify promising candidated. The latter will be tested in a continuous aging reactor to evaluate their resistance to deactivation under col-liquefaction and extract upgrading conditions. Cold flow ebullation tests of catalysts of different head size are presented, along with some screening and crying of experimental catalysts. Spherical methods for examining catalysts are described.

  16. Nitrogen release during coal combustion

    SciTech Connect

    Baxter, L.L.; Mitchell, R.E.; Fletcher, T.H.; Hurt, R.H.

    1995-02-01

    Experiments in entrained flow reactors at combustion temperatures are performed to resolve the rank dependence of nitrogen release on an elemental basis for a suite of 15 U.S. coals ranging from lignite to low-volatile bituminous. Data were obtained as a function of particle conversion, with overall mass loss up to 99% on a dry, ash-free basis. Nitrogen release rates are presented relative to both carbon loss and overall mass loss. During devolatilization, fractional nitrogen release from low-rank coals is much slower than fractional mass release and noticeably slower than fractional carbon release. As coal rank increases, fractional nitrogen release rate relative to that of carbon and mass increases, with fractional nitrogen release rates exceeding fractional mass and fractional carbon release rates during devolatilization for high-rank (low-volatile bituminous) coals. At the onset of combustion, nitrogen release rates increase significantly. For all coals investigated, cumulative fractional nitrogen loss rates relative to those of mass and carbon passes through a maximum during the earliest stages of oxidation. The mechanism for generating this maximum is postulated to involve nascent thermal rupture of nitrogen-containing compounds and possible preferential oxidation of nitrogen sites. During later stages of oxidation, the cumulative fractional loss of nitrogen approaches that of carbon for all coals. Changes in the relative release rates of nitrogen compared to those of both overall mass and carbon during all stages of combustion are attributed to a combination of the chemical structure of coals, temperature histories during combustion, and char chemistry.

  17. Cooperative Research Program in Coal-Waste Liquefaction

    SciTech Connect

    Gerald Huffman

    2000-03-31

    The results of a feasibility study for a demonstration plant for the liquefaction of waste plastic and tires and the coprocessing of these waste polymers with coal are presented. The study was conducted by a committee that included nine representatives from the CFFS, six from the U.S. Department of Energy - Federal Energy Technology Center (FETC), and four from Burns and Roe, Inc. The study included: (1) An assessment of current recycling practices, particularly feedstock recycling in Germany; (2) A review of pertinent research, and a survey of feedstock availability for various types of waste polymers; and (3) A conceptual design for a demonstration plant was developed and an economic analysis for various feedstock mixes. The base case for feedstock scenarios was chosen to be 200 tons per day of waste plastic and 100 tons per day of waste tires. For this base case with oil priced at $20 per barrel, the return on investment (ROI) was found to range from 9% to 20%, using tipping fees for waste plastic and tires typical of those existing in the U.S. The most profitable feedstock appeared to waste plastic alone, with a plant processing 300 t/d of plastic yielding ROI's from 13 to 27 %, depending on the tipping fees for waste plastic. Feedstock recycling of tires was highly dependent on the price that could be obtained for recovered carbon. Addition of even relatively small amounts (20 t/d) of coal to waste plastic and/or coal feeds lowered the ROI's substantially. It should also be noted that increasing the size of the plant significantly improved all ROI's. For example, increasing plant size from 300 t/d to1200 t/d approximately doubles the estimated ROI's for a waste plastic feedstock.

  18. Corrosion of fractionation towers in coal liquefaction plants

    SciTech Connect

    Bagga, P.S.; Harris, C.F.; Baumert, K.L.

    1983-09-01

    Severe corrosion has been observed in the fractionating towers at the Wilsonville, Alabama Advanced Coal Liquefaction Facility and at the Ft. Lewis, Washington Pilot Plant. At Wilsonville, the high corrosion rate of carbon and of types 304 and 316 stainless steel occurred when the facility was processing coal with 0.15 to 0.39 wt % chloride. This corrosion was most severe in the 440 to 485/sup 0/F (225 to 250/sup 0/C) boiling range. The analysis of scale on coupons immersed in the tower showed a high concentration of water-soluble chloride. The analysis of organic compounds in the tower liquids revealed a large amount of acid fractions like phenols and cresols, and basic fractions like aniline. During lab experiments with liquids rich in chlorides and acid and basic fractions, a high corrosion rate was observed. Absence of one or more of these fractions resulted in negligible corrosion. Based on these observations, it is concluded that when water-soluble chlorides, basic nitrogen compounds (basic fractions), and phenols (acid fractions) are simultaneously present in the coal liquids, they exhibit a synergism that results in high corrosivity. In order to reduce the corrosion to acceptable levels, it is recommended that 904L and 317 stainless steel be used as the material of construction for the fractionation tower. It is also recommended that a chloride removal scheme be employed; the scheme would combine removal of chlorides before they reach the tower and a small side draw from the tower. 14 references, 11 figures, 8 tables.

  19. Kinetics assisted design of catalysts for coal liquefaction. Final report

    SciTech Connect

    Klein, M.T.; Foley, H.C.; Calkins, W.H.; Scouten, C.

    1998-02-01

    The thermal and catalytic reactions of 4-(1-naphthylmethyl)bibenzyl (NBBM), a resid and coal model compound, were examined. Catalytic reaction of NBBM was carried out at 400 C under hydrogen with a series of transition metal-based catalytic materials including Fe(CO){sub 4}PPh{sub 3}, Fe(CO){sub 3}(PPh{sub 3}){sub 2}, Fe(CO){sub 2}(PPh{sub 3}){sub 2}CS{sub 2}, Fe(CO){sub 5}, Mo(CO){sub 6}, Mn{sub 2}(CO){sub 10}, Fe{sub 2}O{sub 3} and MoS{sub 2}. Experimental findings and derived mechanistic insights were organized into molecular-level reaction models for NBBM pyrolysis and catalysis. Hydropyrolysis and catalysis reaction families occurring during NBBM hydropyrolysis at 420 C were summarized in the form of reaction matrices which, upon exhaustive application to the components of the reacting system, yielded the mechanistic reaction model. Each reaction family also had an associated linear free energy relationship (LFER) which provided an estimate of the rate constant k{sub i} given a structural property of species i or its reaction. Including the catalytic reaction matrices with those for the pyrolysis model provided a comprehensive NBBM catalytic reaction model and allowed regression of fundamental LFER parameters for the catalytic reaction families. The model also allowed specification of the property of an optimal catalyst. Iron, molybdenum and palladium were predicted to be most effective for model compound consumption. Due to the low costs associated with iron and its disposal, it is a good choice for coal liquefaction catalysis and the challenge remains to synthesize small particles able to access the full surface area of the coal macromolecule.

  20. Coal-derived promoters for the liquefaction of Illinois coal. Final technical report, September 1, 1991--August 31, 1992

    SciTech Connect

    Carty, R.H.; Knight, R.A.

    1992-12-31

    The objective of this program was to investigate the use of liquids derived from coal either by mild gasification or supercritical extraction (SCE) to promote direct liquefaction of Illinois coal. In this two-year program recently developed molecular probe techniques were used to assess the activity of three coal-derived liquids with respect to accelerating (A) hydrogen transfer, (B) carbon-carbon bond cleavage, (C) free radical flux, and (D) hydrocracking activity. Three sample liquids were prepared from IBC-106 coal by: mild gasification in an isothermal free-fall reactor (IFFR), steam treatment/mild gasification in a fixed-bed reactor (ST/FBR), and SCE using toluene. For comparison, tests were also performed on a Wilsonville recycle solvent (RS) and on benzyl phenyl sulfide (BPS), a ``benchmark`` promoter. Sample/blank pairs were tested at 400--425{degrees}C in laboratory microreactors, and effectiveness was based on the increase in extent of a key reaction for each sample containing coal liquid, compared to its blank. In general, the IFFR liquid was the most effective liquid for promoting hydrogen transfer (+21%) and free radical flux (+107%), while the SCE liquid was the most effective promoter of C-C bond cleavage selectivity (+119%) and hydrocracking (+359%). The ST/FBR liquid was slightly less effective than the IFFR liquid in all categories. BPS was used primarily to validate the adequacy of the methods.

  1. Tritium as a tracer in coal liquefaction. 1; Hydrogen mobility of tetralin under coal liquefaction conditions

    SciTech Connect

    Kabe, T.; Ishihara, A.; Daita, Y. )

    1991-08-01

    In this paper the reaction of tetralin with tritiated molecular hydrogen is carried out at 350-440{degrees} C, 20-60 kg/cm{sup 2} for 0-8 h to estimate the hydrogen mobility of tetralin itself. Under these conditions, tetralin is converted to 1-methylindan, naphthalene and n-butylbenzene, and 1-methylindan is a main product. With a rise in temperature and a passage of time, the amount of tritium transferred from the gas phase into tetralin increased and the hydrogen-exchange ratio of tetralin at 440{degrees} C, 120 min and 400{degrees}C, 480 min reached 14.3% and 13.5%, respectively. The hydrogen-exchange ratio and the amount of methylindan increased with a hydrogen/tetralin molar ratio. The addition of coal enhanced the hydrogen exchange between gas phase and tetralin. In the absence and presence of coal, tritium was observed in the isolated naphthalene. It is suggested that hydrogen in tetralin changing to naphthalene may be able to exchange with molecular hydrogen.

  2. Coal liquefaction process streams characterization and evaluation. Topical report: Analytical methods for application to coal-derived resids, A literature survey

    SciTech Connect

    Brandes, S.D.

    1993-06-01

    This literature survey was conducted to address an important question: What are the methods available in the realm of analytical chemistry that may have potential usefulness to the development of coal liquefaction technology? In an attempt to answer to that question, the emphasis of this survey was directed at analytical techniques which would be applicable to the high molecular weight, non-distillable residue of coal-derived liquids. It is this material which is most problematic to the analytical investigator and the developer of direct coal liquefaction processes. A number of comprehensive analytical reviews of literature dealing with coal and other fossil fuels are available. This literature survey will (1) be limited to articles published between 1980--1991, with some exceptions; (2) be limited to the use of analytical methods for high molecular weight, primarily nondistillable, fossil fuel-derived materials, except where the application of an analytical method to coals or distillates may show promise for application to non-distillable coal-derived materials; and (3) demonstrate the potential usefulness of an analytical method by showing how the method has been applied to high molecular weight, non-distillable materials, if not specifically to coal liquids. The text is divided by type of methodology, i.e. spectroscopy, microscopy, etc. Each section will be essentially free-standing. An historical background is provided.

  3. Exploratory research on solvent-refined-coal liquefaction. Annual technical progress report, January 1-December 31, 1980

    SciTech Connect

    1981-04-01

    This report summarizes the progress of the Exploratory Research on Solvent Refined Coal Liquefaction project by the Pittsburg and Midway Coal Mining Co.'s Merriam Laboratory during 1980. Six coals and a coal blend, representing the Interior, Rocky Mountain, Eastern and Northern Great Plains Provinces, were processed in the SRC I and SRC II modes to study the relationship between coal properties and liquefaction behavior. Disposable catalysts and specific compounds were added to Loveridge, Kaiparowits and Blacksville No. 2 coals during SRC II mode liquefaction. Kentucky 9/14, Indiana V and Loveridge coals were processed at short residence times (4 to 9 minutes) in the SRC I mode to evaluate the effects of temperature, pressure, residence time and disposable catalyst addition. Finally, coal from the Powhatan No. 1 Mine was evaluated as a feedstock for major coal liquefaction facilities.

  4. Design, synthesis, and characterization of novel fine-particle, unsupported catalysts for coal liquefaction

    SciTech Connect

    Klein, M.T.

    1991-02-22

    The first task in our proposed study of catalysts for coal liquefaction was to prepare ultrafine dispersed metal sulfide particles by reactive precipitation from solutions of appropriate metal precursors. At this point, equipment to allow us to prepare these air-sensitive materials in an anaerobic environment has been acquired and assembled. Initial experiments aimed at synthesizing iron sulfide particles have been initiated. As part of the investigation of short contact time catalytic coal liquefaction, initial efforts focused on the noncatalytic pyrolysis reactions of coal and a model compound, Dibenzyl ether (DBE). Two different reactor configurations were examined; catalytic experiments are planned for the coming month.

  5. Low severity coal liquefaction promoted by cyclic olefins. Quarterly report, April--June, 1995

    SciTech Connect

    Curtis, C.W.

    1996-01-01

    The goal of this research is to develop a methodology for analyzing the reactivity of cyclic alkenes in situ in a high temperature and high pressure infrared cell. Cyclic alkenes are highly reactive donors of hydrogen to coal in low severity coal liquefaction.

  6. Fundamental studies of retrograde reactions in direct liquefaction

    SciTech Connect

    Serio, M.A.; Solomon, P.R.; Kroo, E.; Charpenay, S.; Bassilakis, R.

    1991-12-17

    The overall objective of the program was to improve the understanding of retrograde reactions and their dependencies on coal rank and structure, and/or coal modifications and reaction conditions. Because retrograde reactions are competitive with bond breaking reactions, an understanding of both is required to shift the competition in favor of the latter. Related objectives were to clarify the conflicting observations reported in literature on such major topics as the role of oxygen groups in retrograde reactions and to provide a bridge from very fundamental studies on pure compounds to phenomenological studies on actual coal. This information was integrated into the FG-DVC model, which was improved and extended to the liquefaction context.

  7. Determination of unconverted HDPE in coal/plastics co-liquefaction stream samples

    SciTech Connect

    Robbins, G.A.; Winschel, R.A.; Burke, F.P.

    1996-12-31

    In several coal/plastics liquefaction runs performed by Hydrocarbon Technologies, Inc. (HTI), a substantial amount of incompletely converted high-density polyethylene (HDPE) was present in ash-free recycle resid streams when either the ROSE-SR unit was used in Run POC-2, or the pressure filter unit was used in Runs CMSL-8 and CMSL-9. This indicates that the HDPE is less reactive than coal at the liquefaction conditions used. In these ash-free streams, there is no solid organic or inorganic material arising from the coal, and the incompletely converted HDPE can be recovered by extraction and filtration with tetrahydrofuran (THF) at room temperature. The HDPE (or HDPE-like material, which could also consist of heavy waxes) is THF insoluble. However, in ashy streams, there are both inorganic ({open_quotes}ash{close_quotes}) and organic (unconverted coal) components present from liquefaction of the coal, that interfere with an easy and clean separation of the HDPE from the coal/plastics liquefaction stream sample. Therefore, CONSOL developed an analytical procedure for HDPE in the ashy stream samples based on extraction of HDPE from the sample using hot (150{degrees}C) decalin (decahydronaphthalene), in which the HDPE is soluble. The decalin extraction is both preceded and succeeded by extractions and washes with THF at room temperature, to remove the coal-derived components from the sample.

  8. Steam pretreatment for coal liquefaction. Sixth quarterly report, 1 January 1992--31 March 1992

    SciTech Connect

    Graff, R.A.; Balogh-Nair, V.

    1992-06-28

    Steam pretreatment is the reaction of coal with steam at temperatures well below those usually used for solubilization. The objective of the proposed work is to test the application of steam pretreatment to coal liquefaction. Conversion of the autoclave apparatus to rapid heating liquefaction was carried out this quarter following redesign of the coal slurry injection system. The modified equipment and procedure was tested in a simulated liquefaction run without coal. Initial tests of slurried {minus}20 mesh coal showed too rapid settling for successful operation. Coal ground to pass 200 mesh proved suitable, and a impact grinder was put into operation to grind the material under an inert atmosphere. A batch of Illinois No. 6 coal for the, first rapid heating liquefaction tests has been prepared and stored under inert gas. The steam pretreatment of {alpha}-benzylnaphthyl ether was carried out using stainless steel and glass lined reactors. A preparative scale procedure for product separation was developed. The major components were identified and the average product distribution determined for both types of reactors. Pretreatment of {alpha}-naphthylmethyl phenyl ether was also carried out using stainless steel and glass-lined reactors. Separation and analysis of the products has been started. The major components have been identified. Analyses and identification of the components will be continued next quarter.

  9. ENVIRONMENTAL AND ECONOMIC ASPECTS OF INDIRECT COAL LIQUEFACTION PROCESSES: A REPORT EMPHASIZING THE RELATIONSHIP BETWEEN PRODUCT MIX AND EFFICIENCY

    EPA Science Inventory

    This report covers environmental and economic aspects of three indirect liquefaction processes. Specifically, the following are addressed: U.S. coal resources; the Lurgi/Methanol, Lurgi/Methanol/Mobil M, and the Lurgi/Fischer-Tropsch indirect coal liquefaction processes; and envi...

  10. Bimetallic promotion of cooperative hydrogen transfer and heteroatom removal in coal liquefaction

    SciTech Connect

    Eisch, J.J.

    1991-07-01

    The ultimate objective of this research is to uncover new catalytic processes for the liquefaction of coal and for upgrading coal-derived fuels by removing undesirable organosulfur, organonitrogen and organooxygen constituents. Basic to both the liquefaction of coal and the purification of coal liquids is the transfer of hydrogen from such sources as dihydrogen, metal hydrides or partially reduced aromatic hydrocarbons to the extensive aromatic rings in coal itself or to aromatic sulfides, amines or ethers. Accordingly, this study is exploring how such crucial hydrogen-transfer processes might be catalyzed by soluble, low-valent transition metal complexes and/or Lewis acids under moderate conditions of temperature and pressure. By learning the mechanism whereby H{sub 2}, metal hydrides or partially hydrogenated aromatics do transfer hydrogen to model aromatic compounds, with the aid of homogeneous, bimetallic catalysts, we hope to identify new methods for producing superior fuels from coal.

  11. Bimetallic promotion of cooperative hydrogen transfer and heteroatom removal in coal liquefaction

    SciTech Connect

    Eisch, J.J.

    1991-10-01

    The ultimate objective of this research is to uncover new catalytic processes for the liquefaction of coal and for upgrading coal-derived fuels by removing undesirable organosulfur, organonitrogen and organooxygen constituents. Basic to both the liquefaction of coal and the purification of coal liquids is the transfer of hydrogen from such sources as dihydrogen, metal hydrides or partially reduced aromatic hydrocarbons to the extensive aromatic rings in coal itself or to aromatic sulfides, amines or ethers. Accordingly, this study is exploring how such crucial hydrogen-transfer processes might be catalyzed by soluble, low-valent transition metal complexes and/or Lewis acids under moderate conditions of temperature and pressure. By learning the mechanism whereby H{sub 2}, metal hydrides or partially hydrogenated aromatics do transfer hydrogen to model aromatic compounds, with the aid of homogeneous, bimetallic catalysts, we hope to identify new methods for producing superior fuels from coal.

  12. Coal liquefaction process streams characterization and evaluation: High performance liquid chromatography (HPLC) of coal liquefaction process streams using normal-phase separation with uv diode array detection

    SciTech Connect

    Clifford, D.J.; McKinney, D.E.; Hou, Lei; Hatcher, P.G.

    1994-01-01

    This study demonstrated the considerable potential of using two-dimensional, high performance liquid chromatography (HPLC) with normal-phase separation and ultraviolet (UV) diode array detection for the examination of filtered process liquids and the 850{degrees}F{sup {minus}} distillate materials derived from direct coal liquefaction process streams. A commercially available HPLC column (Hypersil Green PAH-2) provided excellent separation of the complex mixture of polynuclear aromatic hydrocarbons (PAHs) found in coal-derived process streams process. Some characteristics of the samples delineated by separation could be attributed to processing parameters. Mass recovery of the process derived samples was low (5--50 wt %). Penn State believes, however, that, improved recovery can be achieved. High resolution mass spectrometry and gas chromatography/mass spectrometry (GC/MS) also were used in this study to characterize the samples and the HPLC fractions. The GC/MS technique was used to preliminarily examine the GC-elutable portion of the samples. The GC/MS data were compared with the data from the HPLC technique. The use of an ultraviolet detector in the HPLC work precludes detecting the aliphatic portion of the sample. The GC/MS allowed for identification and quantification of that portion of the samples. Further development of the 2-D HPLC analytical method as a process development tool appears justified based on the results of this project.

  13. ADVANCED DIRECT LIQUEFACTION CONCEPTS FOR PETC GENERIC UNITS

    SciTech Connect

    Adam J. Berkovich

    2000-03-01

    The results of Laboratory and Bench-Scale experiments and supporting technical and economic assessments conducted under DOE Contract No. DE-AC22-91PC91040 is reported for the period April 1, 1998 to June 30, 1998. This contract is with the University of kentucky Research Foundation, which supports work with the University of Kentucky Center for Applied Energy Researc, CONSOL, Inc., LDP Associates, and Hydrocarbon Technologies, Inc. This work involves the introduction into the basic two-stage liquefaction process several novel concepts, which include dispersed lower-cost catalysts, coal cleaning by oil agglomeration, and distillate hydrotreating and dewaxing.

  14. Advanced Direct Liquefaction Concepts for PETC Generic Units - Phase II

    SciTech Connect

    1997-02-01

    Reported here are the results of Laboratory and Bench-Scale experiments and supporting technical and economic assessments conducted under DOE Contract No. DE-AC22-91PC9104O during the period October 1, 1996 to December 31, 1996. This contract is with the University of Kentucky Research Foundation which supports work with the University of Kentucky Center for Applied Energy Research, CONSOI+ Inc., LDP Associates, and Hydrocarbon Technologies, Inc. This work invoives the introduction into the basic two stage liquefaction process several novel concepts which include dispersed lower-cost catalysts, coal cleaning by oil agglomeration, and distillate hydrotreating and dewaxing.

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

    SciTech Connect

    Song, C.; Cooke, W.S.; Schmidt, E.; Schobert, H.H.

    1996-02-01

    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.

  16. The Wilsonville Advanced Coal Liquefaction Research and Development Facility, Wilsonville, Alabama

    SciTech Connect

    Not Available

    1990-05-01

    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 catalysts were used to improve coal liquefaction reactions and nickel-molybdenum catalysts were used in the hydrotreater. 28 refs., 31 figs., 13 tabs.

  17. A Characterization and Evaluation of Coal Liquefaction Process Streams. Results of Inspection Tests on Nine Coal-Derived Distillation Cuts in the Jet Fuel Boiling Range

    SciTech Connect

    S. D. Brandes; R. A. Winschel

    1999-12-30

    This report describes the assessment of the physical and chemical properties of the jet fuel (180-300 C) distillation fraction of nine direct coal liquefaction products and compares those properties to the corresponding specifications for aviation turbine fuels. These crude coal liquids were compared with finished fuel specifications specifically to learn what the refining requirements for these crudes will be to make them into finished fuels. The properties of the jet fuel fractions were shown in this work to require extensive hydrotreating to meet Jet A-1 specifications. However, these materials have a number of desirable qualities as feedstocks for the production of high energy-density jet fuels.

  18. [A Quick Quantitative Analysis for Group Composition of Coal Liquefaction Oil by Ultraviolet Spectroscopy].

    PubMed

    Fan, Wen-jun; Wu, Mei-xiang; Hao, Jian-shu; Feng, Jie; Li, Wen-ying

    2015-07-01

    Gas chromatography is now the primary analysis method for the coal liquefaction oil. However, a simple and rapid quantification/qualification of the coal liquefaction oil can hardly be realized, because the coal liquefaction oil is in a heterogeneous state with a long boiling range. The aim of this study was to establish a rapid and accurate method for the quantification of phenolic compounds, aromatics and aliphatic hydrocarbons in coal liquefaction oil. A representative composition of coal liquefaction light oil, i.e., the distillate fractions of the boiling point range 180-200 degrees C, was chosen as the investigated object. The characteristic absorption peaks of the samples in the UV spectra (200-400 nm) were examined, using three kinds of solvents, cyclohexane, ethanol, 50 Wt% NaOH/ethanol mixture. Among them, the mixture solvent provided the best performance, where the aromatics interfered minimally with the quantification of phenolic compounds by avoiding the peak overlapping problem. By comparison of the UV absorption standard curves between the standard compounds (phenol, m-cresol, p-cresol and o-cresol) and the phenolic mixtures in coal liquefaction oil, m-cresol was selected for the quantification of phenolic compounds in coal liquefaction oil. The content of phenolic compounds was determined to be 32.14% according to the calibration curve of m-cresol at 290 nm, and this result is largely consistent with that determined by weighing after separation. Based on UV and GC analysis of the dephenolized oil, the standard curve of tetrahydronaphthalene at 266 nm was used for the quantification of aromatic hydrocarbons in coal liquefaction oil. The contents of aromatic and aliphatic hydrocarbons were determined to be 44.91% and 22.95%, respectively. To verify the accuracy of the method, recovery of added standards in the oil samples was determined and found to be 104.3%-110.75% and 84.3%-91.75% for phenolic compounds and aromatics, respectively. These results

  19. Catalyst system and process for benzyl ether fragmentation and coal liquefaction

    DOEpatents

    Zoeller, Joseph Robert

    1998-04-28

    Dibenzyl ether can be readily cleaved to form primarily benzaldehyde and toluene as products, along with minor amounts of bibenzyl and benzyl benzoate, in the presence of a catalyst system comprising a Group 6 metal, preferably molybdenum, a salt, and an organic halide. Although useful synthetically for the cleavage of benzyl ethers, this cleavage also represents a key model reaction for the liquefaction of coal; thus this catalyst system and process should be useful in coal liquefaction with the advantage of operating at significantly lower temperatures and pressures.

  20. Heavy recycle solvent studies in two-stage coal liquefaction. Final technical report, September 1, 1982-December 30, 1983

    SciTech Connect

    Longanbach, J. R.

    1984-01-10

    The objective of this program has been to study the chemistry of the components with high boiling points in a direct coal liquefaction recycle solvent and to identify those components which lead to higher overall yields and improved product stability in the initial coal dissolution step of direct coal liquefaction processes. The major conclusions are: -454 C recycle solvent is primarily aromatic hydrocarbons (73%) and contains almost no asphaltenes; +454 C recycle solvent is primarily asphaltenes and aromatic hydrocarbons; recycle solvent also contains aliphatic hydrocarbons, N-containing aromatics and O-containing aromatics; heteroatoms in coal derived materials seem to be grouped by type, i.e. acidic O and basic N and sulfur occur together; under helium a small net amount of hydrogen and more CO and CO/sub 2/ are produced than under hydrogen; under hydrogen the amounts of H/sub 2/S and hydrocarbon gases are increased and a small amount of hydrogen gas is usually consumed; overall coal conversions to THF solubles are improved by adding more -454 C solvent but decreased by adding +454 C solvent; for added fractions of -454 C solvent the pecent conversion to THF solubles increases in the order aromatic hydrocarbons (+7.2) > aliphatic hydrocarbons (+0.8) > no added solvent (0.0) > N-containing aromatics (-0.9) > O-containing aromatics (-22.1); percent conversion to THF solubles using -454 C solvent with +454 C solvent fractions added decrease in the order aliphatics (+3.7) > aromatic hydrocarbons (+3.0) > no added solvent (0.0) > O-containing aromatics (-9.3) > N-containing aromatics (-13.3); of the +454 C solvent components, aromatic hydrocarbons and aliphatic hydrocarbons are beneficial but total only approx. 25% of the +454 C recycle solvent; and steric effects may be important in determining the effectiveness of the heavier solvent components as liquefaction solvents. 28 references, 25 figures, 31 tables.

  1. Permeation by liquefied coal of gloves used in coal liquefaction pilot plants

    SciTech Connect

    Bennett, R.D.; Feigley, C.E.; Oswald, E.O.; Hill, R.H.

    1983-01-01

    The protective capabilities of PVC, natural rubber and milled nitrile rubber gloves currently used in coal liquefaction pilot plants were assessed and the effectiveness of a laundering method was evaluated. The breakthrough times and cumulative permeation for exposure to toluene and to liquefied coal were determined by measurement of radiolabeled phenol tracer in the aqueous receiving medium. Breakthrough times, normalized by division by the square of the material thickness, agreed with the findings of other studies. On exposure to liquefied coal, the nitrile laboratory glove resisted breakthrough the longest (between 12 and 24 hours), although it was the thinnest material tested. Breakthrough times for the other gloves ranged from 2.75 to 6.5 hours with the times for the natural rubber glove materials intermediate to the two PVC glove materials tested. However, when normalized for thickness, both PVC materials were more resistant to breakthrough than rubber. It was found that the laundering method did not completely decontaminate samples of PVC glove material pre-exposed to liquefied coal for 24 hours under laboratory conditions.

  2. Short residence time coal liquefaction process including catalytic hydrogenation

    DOEpatents

    Anderson, Raymond P.; Schmalzer, David K.; Wright, Charles H.

    1982-05-18

    Normally solid dissolved coal product and a distillate liquid product are produced by continuously passing a feed slurry comprising raw feed coal and a recycle solvent oil and/or slurry together with hydrogen to a preheating-reaction zone (26, alone, or 26 together with 42), the hydrogen pressure in the preheating-reaction zone being at least 1500 psig (105 kg/cm.sup.2), reacting the slurry in the preheating-reaction zone (26, or 26 with 42) at a temperature in the range of between about 455.degree. and about 500.degree. C. to dissolve the coal to form normally liquid coal and normally solid dissolved coal. A total slurry residence time is maintained in the reaction zone ranging from a finite value from about 0 to about 0.2 hour, and reaction effluent is continuously and directly contacted with a quenching fluid (40, 68) to substantially immediately reduce the temperature of the reaction effluent to below 425.degree. C. to substantially inhibit polymerization so that the yield of insoluble organic matter comprises less than 9 weight percent of said feed coal on a moisture-free basis. The reaction is performed under conditions of temperature, hydrogen pressure and residence time such that the quantity of distillate liquid boiling within the range C.sub.5 -454.degree. C. is an amount at least equal to that obtainable by performing the process under the same condition except for a longer total slurry residence time, e.g., 0.3 hour. Solvent boiling range liquid is separated from the reaction effluent (83) and recycled as process solvent (16). The amount of solvent boiling range liquid is sufficient to provide at least 80 weight percent of that required to maintain the process in overall solvent balance.

  3. Short residence time coal liquefaction process including catalytic hydrogenation

    DOEpatents

    Anderson, R.P.; Schmalzer, D.K.; Wright, C.H.

    1982-05-18

    Normally solid dissolved coal product and a distillate liquid product are produced by continuously passing a feed slurry comprising raw feed coal and a recycle solvent oil and/or slurry together with hydrogen to a preheating-reaction zone, the hydrogen pressure in the preheating-reaction zone being at least 1,500 psig (105 kg/cm[sup 2]), reacting the slurry in the preheating-reaction zone at a temperature in the range of between about 455 and about 500 C to dissolve the coal to form normally liquid coal and normally solid dissolved coal. A total slurry residence time is maintained in the reaction zone ranging from a finite value from about 0 to about 0.2 hour, and reaction effluent is continuously and directly contacted with a quenching fluid to substantially immediately reduce the temperature of the reaction effluent to below 425 C to substantially inhibit polymerization so that the yield of insoluble organic matter comprises less than 9 weight percent of said feed coal on a moisture-free basis. The reaction is performed under conditions of temperature, hydrogen pressure and residence time such that the quantity of distillate liquid boiling within the range C[sub 5]-454 C is an amount at least equal to that obtainable by performing the process under the same condition except for a longer total slurry residence time, e.g., 0.3 hour. Solvent boiling range liquid is separated from the reaction effluent and recycled as process solvent. The amount of solvent boiling range liquid is sufficient to provide at least 80 weight percent of that required to maintain the process in overall solvent balance. 6 figs.

  4. Examination of alternative catalysts for biomass direct liquefaction

    SciTech Connect

    Tran, A.D.; Rogers, D.Z.

    1985-08-01

    We have now completed a survey study of several water-soluble salts of transition metals that are deemed likely to have utility as catalysts for direct biomass liquefaction in a carbon monoxide steam process. Certain salts of molybdenum and nickel are the most effective catalysts, and are the only species for which some catalytic activity independent of the ligand can be shown. The most effective forms of the nickel and molybdenum are cyanide and oxyanion complexes. 30 refs., 5 figs., 4 tabs.

  5. Advanced direct liquefaction concepts for PETC generic units. Quarterly technical progress report, January--March 1992

    SciTech Connect

    Not Available

    1992-04-01

    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.

  6. Steam pretreatment for coal liquefaction. Final report, September 26, 1990--March 18, 1995

    SciTech Connect

    Graff, R.A.; Balogh-Nair, V.; Ivanenko, O.; Brathwaite, C.

    1995-10-16

    The objective of this study is to demonstrate the use of subcritical steam to pretreat coal for slurry liquefaction, allowing liquefaction to be carried out at lower severity and improving product yield and quality. Samples of Illinois No. 6 coal were pretreated in 750 psia steam at 340{degree}C for 15 minutes. These samples, as well as raw coal, were liquefied at high (400{degree}C, 30 min.) and low (385{degree}C, 15 min.) severity conditions under 1500 psia hydrogen with tetralin as the donor solvent. Improved yields were obtained at both conditions. (Improved yields were not obtained at a liquefaction temperature of 350{degree}C as that put the sample into the region of retrogressive reactions). The deleterious effects of slow heating and exposure of the sample to air were demonstrated. Under low severity conditions, steam pretreatment more that doubled the oil yield, increasing it from 12.5 to 29 wt %. Tests were also conducted with aromatic ethers as model compounds. These were exposed to inert gas and steam at pretreatment conditions and in some cases to liquid water at 315{degree}C. {alpha}-Benzylnaphthyl ether and {alpha}- naphthylmethyl phenyl ether show little difference in conversion and product distribution when the thermolysis atmosphere is changed from inert gas to steam. However when these compounds were reacted in the presence of 5 {angstrom} zeolite, the yields of the thermolysis products improved. Zeolite proved effective in suppressing isomerization of the starting materials. These results suggested that zeolites might be beneficial in steam pretreatment of coal and in coal liquefaction. Pretreatment and liquefaction of mixtures of coal and zeolites increases yields of asphaltenes and preasphaltenes.

  7. Coal liquefaction and oil upgrading process to obtain maximum yield of distillate

    SciTech Connect

    Gleim, W.K.

    1981-12-22

    A portion of higher O/sub 2/ content lignite or brown coal is mixed with bituminous coal to provide exothermic conditions and reduce extraneous heat to the liquefaction reactor. In addition, with a crude oil carrying stream for the coal to the reactor there can be conversion at the controlled heating of 380/sup 0/ to 400/sup 0/ C, and in the presence of H/sub 2/c and CO at 100 to 200 atmospheres a maximizing of distillate from the crude and a high conversion of coal to liquified distillate.

  8. Method for separating liquid and solid products of liquefaction of coal or like carbonaceous materials

    DOEpatents

    Malek, John M.

    1978-04-18

    A method of improving the quality of slurry products taken from coal liquefaction reactors comprising subjecting the slurry to treatment with an alkaline compound such as caustic soda in the presence of steam in order to decompose the phenolic and acidic materials present in the slurry, and to also lower the slurry viscosity to allow separation of solid particles by sedimentation.

  9. Solvent tailoring in coal liquefaction. Quarterly report, April-June 1984

    SciTech Connect

    Tarrer, A.R.; Curtis, C.W.; Guin, J.A.; Williams, D.C.

    1984-07-01

    Although the numerous functions of the solvent during liquefaction are not completely understood, the provision for (and the maintenance of) an effective process solvent is necessary for effective coal liquefaction. In this project, the function of the process solvent regarding vapor-liquid equilibrium, hydrogen donation, and catalyst activity has been explored. In previously reported work, a number of donor compounds were evaluated for their relative efficiency in converting coal to cresol solubles. Attempts to correlate the relative efficiency of the various donor compounds were made on the basis of thermodynamic stability and structural features of the molecules. Currently, work is underway with selected donor compounds to determine if the chemical nature of the compound influences the product distribution obtained during coal liquefaction as well as affecting the amount of conversion obtained. The product distribution, which is being used to evaluate the liquefaction products, is based upon extraction of the products into different solvents. The products are divided into oil, pentane soluble material; asphaltenes, pentane insoluble, benzene soluble material; preasphaltenes, benzene insoluble, methylene chloride/methanol soluble material; and insoluble organic matter, methylene chloride/methanol insoluble material. The effectiveness of the hydrogen donor solvent will be measured by the amount of higher quality material (oil and asphaltenes) obtained as well as by the amount of coal converted.

  10. Separating liquid and solid products of liquefaction of coal or like carbonaceous materials

    DOEpatents

    Malek, John M.

    1979-06-26

    Slurryform products of coal liquefaction are treated with caustic soda in presence of H.sub.2 O in an inline static mixer and then the treated product is separated into a solids fraction and liquid fractions, including liquid hydrocarbons, by gravity settling preferably effected in a multiplate settling separator with a plurality of settling spacings.

  11. Development of an extruder-feeder biomass direct liquefaction process

    SciTech Connect

    White, D.H.; Wolf, D. . Dept. of Chemical Engineering)

    1991-10-01

    As an abundant, renewable, domestic energy resource, biomass could help the United States reduce its dependence on imported oil. Biomass is the only renewable energy technology capable of addressing the national need for liquid transportation fuels. Thus, there is an incentive to develop economic conversion processes for converting biomass, including wood, into liquid fuels. Through research sponsored by the US DOE's Biomass Thermochemical Conversion Program, the University of Arizona has developed a unique biomass direct liquefaction system. The system features a modified single-screw extruder capable of pumping solid slurries containing as high as 60 wt% wood flour in wood oil derived vacuum bottoms at pressures up to 3000 psi. The extruder-feeder has been integrated with a unique reactor by the University to form a system which offers potential for improving high pressure biomass direct liquefaction technology. The extruder-feeder acts simultaneously as both a feed preheater and a pumping device for injecting wood slurries into a high pressure reactor in the biomass liquefaction process. An experimental facility was constructed and following shakedown operations, wood crude oil was produced by mid-1985. By July 1988, a total of 57 experimental continuous biomass liquefaction runs were made using White Birch wood feedstock. Good operability was achieved at slurry feed rates up to 30 lb/hr, reactor pressures from 800 to 3000 psi and temperatures from 350{degree}C to 430{degree}C under conditions covering a range of carbon monoxide feed rates and sodium carbonate catalyst addition. Crude wood oils containing as little as 6--10 wt% residual oxygen were produced. 38 refs., 82 figs., 26 tabs.

  12. Development of an extruder-feeder biomass direct liquefaction process

    SciTech Connect

    White, D.H.; Wolf, D. . Dept. of Chemical Engineering)

    1991-10-01

    As an abundant, renewable, domestic energy resource, biomass could help the United States reduce its dependence on imported oil. Biomass is the only renewable energy technology capable of addressing the national need for liquid transportation fuels. Thus, there is an incentive to develop economic conversion processes for converting biomass, including wood, into liquid fuels. Through research sponsored by the US DOE's Biomass Thermochemical Conversion Program, the University of Arizona has developed a unique biomass direct liquefaction system. The system features a modified single-screw extruder capable of pumping solid slurries containing as high as 60 wt % wood flour in wood oil derived vacuum bottoms at pressures up to 3,000 psi. By comparison, conventional pumping systems are capable of pumping slurries containing only 10--20 wt % wood flour in wood oil under similar conditions. The extruder-feeder has been integrated with a unique reactor to form a system which offers potential for improving high pressure biomass direct liquefaction technology. The extruder-feeder acts simultaneously as both a feed preheater and a pumping device for injecting wood slurries into a 3,000 psi pressure reactor in the biomass liquefaction process. An experimental facility was constructed during 1983--84. Following shakedown operations, wood crude oil was produced by mid-1985. During the period January 1985 through July 1988, a total of 57 experimental continuous biomass liquefaction runs were made using White Birch wood feedstock. Good operability was achieved at slurry feed rates up to 30 lb/hr, reactor pressures from 800 to 3,000 psi and temperatures from 350{degrees}C to 430{degrees}C under conditions covering a range of carbon monoxide feed rates and sodium carbonate catalyst addition. Crude wood oils containing as little as 6--10 wt % residual oxygen were produced. 43 refs., 81 figs., 52 tabs.

  13. Coal liquefaction and hydrogenation: Processes and equipment. (Latest citations from the US Patent database). Published Search

    SciTech Connect

    Not Available

    1993-07-01

    The bibliography contains citations of selected patents concerning methods, processes, and apparatus for coal liquefaction and hydrogenation. Included are patents for catalytic two-stage, catalytic single-step, fixed-bed, hydrogen-donor, internal heat transfer, and multi-phase processes. Topics also include catalyst production, catalyst recovery, desulfurization, pretreatment of coals, energy recovery processes, solvent product separation, hydrogenating gases, and pollution control. (Contains 250 citations and includes a subject term index and title list.)

  14. Coal liquefaction process streams characterization and evaluation: Estimation of total phenol concentrations in coal liquefaction resids by [sup 31]P NMR spectroscopy

    SciTech Connect

    Mohan, J.T.; Verkade, J.G. )

    1992-11-01

    In this study, Iowa State University researchers used [sub 31]P-tagged reagents to derivatize the labile hydrogen functional groups in the THF-soluble portion of 850[degrees]F[sup +] distillation resid materials and the THF-soluble portion of process oils derived from direct coal liquefaction.[sup 31]P-NMR was used to analyze the derivatized samples. NMR peak assignments can be made by comparison to model compounds similarly derivatized. Species can be quantified by integration of the NMR signals. Different [sup 31]P-NMR tagged reagents can be used to produce different degrees of peak resolution in the NMR spectrum. This, in turn, partially dictates the degree of speciation and/or quantification of species, or classes of compounds, that can be accomplished. Iowa State chose a [sup 31]P-tagged reagent (ClPOCMe[sub 2]CMe[sub 2]O) which was shown previously to be particularly useful in the derivatization of phenols. The derivatized samples all exhibited a small group of peaks attributed to amines and a broad group of peaks in the phenol region. The presence of paramagnetic species in the samples caused the NMR signals to broaden. Electron paramagnetic resonance (EPR) spectra confirmed the presence of paramagnetic organic free radicals in selected samples. Various methods were employed to process the NMR data. The complexity and broadness of the phenol peak, however, made speciation of the phenols impractical.

  15. Coal liquefaction process streams characterization and evaluation: Estimation of total phenol concentrations in coal liquefaction resids by {sup 31}P NMR spectroscopy

    SciTech Connect

    Mohan, J.T.; Verkade, J.G.

    1992-11-01

    In this study, Iowa State University researchers used {sub 31}P-tagged reagents to derivatize the labile hydrogen functional groups in the THF-soluble portion of 850{degrees}F{sup +} distillation resid materials and the THF-soluble portion of process oils derived from direct coal liquefaction.{sup 31}P-NMR was used to analyze the derivatized samples. NMR peak assignments can be made by comparison to model compounds similarly derivatized. Species can be quantified by integration of the NMR signals. Different {sup 31}P-NMR tagged reagents can be used to produce different degrees of peak resolution in the NMR spectrum. This, in turn, partially dictates the degree of speciation and/or quantification of species, or classes of compounds, that can be accomplished. Iowa State chose a {sup 31}P-tagged reagent (ClPOCMe{sub 2}CMe{sub 2}O) which was shown previously to be particularly useful in the derivatization of phenols. The derivatized samples all exhibited a small group of peaks attributed to amines and a broad group of peaks in the phenol region. The presence of paramagnetic species in the samples caused the NMR signals to broaden. Electron paramagnetic resonance (EPR) spectra confirmed the presence of paramagnetic organic free radicals in selected samples. Various methods were employed to process the NMR data. The complexity and broadness of the phenol peak, however, made speciation of the phenols impractical.

  16. Economic aspects of coal gasification and coal liquefaction. January 1972-February 1981 (citations from the International Aerospace Abstracts Data Base). Report for January 1972-February 1981

    SciTech Connect

    Not Available

    1981-03-01

    This retrospective bibliography contains citations concerning coal conversion economic considerations. Economic aspects of coal gasification and coal liquefaction techniques and technology are covered from coal source or supply to fuel production and consumption. Some attention is given to economic comparisons with other fuel sources. (Contains 135 citations fully indexed and including a title list.)

  17. Two-stage coal liquefaction process materials from the Wilsonville Facility operated in the nonintegrated and integrated modes: chemical analyses and biological testing

    SciTech Connect

    Later, D.W.

    1985-01-01

    This document reports the results from chemical analyses and biological testing of process materials sampled during operation of the Wilsonville Advanced Coal Liquefaction Research and Development Facility (Wilsonville, Alabama) in both the noncoupled or nonintegrated (NTSL Run 241) and coupled or integrated (ITSL Run 242) two-stage liquefaction operating modes. Mutagenicity and carcinogenicity assays were conducted in conjunction with chromatographic and mass spectrometric analyses to provide detailed, comparative chemical and biological assessments of several NTSL and ITSL process materials. In general, the NTSL process materials were biologically more active and chemically more refractory than analogous ITSL process materials. To provide perspective, the NTSL and ITSL results are compared with those from similar testing and analyses of other direct coal liquefaction materials from the solvent refined coal (SRC) I, SRC II and EDS processes. Comparisons are also made between two-stage coal liquefaction materials from the Wilsonville pilot plant and the C.E. Lummus PDU-ITSL Facility in an effort to assess scale-up effects in these two similar processes. 36 references, 26 figures, 37 tables.

  18. Wilsonville Advanced Coal Liquefaction Research and Development Facility, Wilsonville, Alabama. Technical progress report, Run 243 with Illinois 6 coal

    SciTech Connect

    Not Available

    1984-02-01

    This report presents the operating results for Run 243 at the Advanced Coal Liquefaction R and D Facility in Wilsonville, Alabama. This run was made in an Integrated Two-Stage Liquefaction (ITSL) mode using Illinois 6 coal from the Burning Star mine. The primary objective was to demonstrate the effect of a dissolver on the ITSL product slate, especially on the net C/sub 1/-C/sub 5/ gas production and hydrogen consumption. Run 243 began on 3 February 1983 and continued through 28 June 1983. During this period, 349.8 tons of coal was fed in 2947 hours of operation. Thirteen special product workup material balances were defined, and the results are presented herein. 29 figures, 19 tables.

  19. Materials performance at the Wilsonville Coal Liquefaction Facility, 1989--1991

    SciTech Connect

    Keiser, J.R. ); Patko, A.J. . Southern Clean Fuels Div.)

    1991-01-01

    The Advanced Coal Liquefaction Research and Development Facility in Wilsonville, Alabama, is funded by the US Department of Energy (DOE), the Electric Power Research Institute (EPRI), and Amoco Corporation. On behalf of these organizations, Southern Company Services manages and Southern Clean Fuels Division of Southern Electric International operates the Wilsonville facility. Oak Ridge National Laboratory (ORNL) receives funding from DOE to provide materials technical support to the Wilsonville operators. For the period July 1987 through November 1990 the plant was operated with two reactors a thermal reactor and a catalytic reactor in a close-coupled integrated two-stage liquefaction mode. Coal processed was obtained from several seams including Ohio No. 6, Illinois No. 6, and Pittsburgh No. 8, as well as Texas lignite and several subbituminous coals. Corrosion samples which were removed for examination at the end of this period were exposed in the vacuum distillation tower, the atmospheric distillation tower, the high pressure separator, and first stage reactor.

  20. Method for controlling boiling point distribution of coal liquefaction oil product

    DOEpatents

    Anderson, R.P.; Schmalzer, D.K.; Wright, C.H.

    1982-12-21

    The relative ratio of heavy distillate to light distillate produced in a coal liquefaction process is continuously controlled by automatically and continuously controlling the ratio of heavy distillate to light distillate in a liquid solvent used to form the feed slurry to the coal liquefaction zone, and varying the weight ratio of heavy distillate to light distillate in the liquid solvent inversely with respect to the desired weight ratio of heavy distillate to light distillate in the distillate fuel oil product. The concentration of light distillate and heavy distillate in the liquid solvent is controlled by recycling predetermined amounts of light distillate and heavy distillate for admixture with feed coal to the process in accordance with the foregoing relationships. 3 figs.

  1. Method for controlling boiling point distribution of coal liquefaction oil product

    DOEpatents

    Anderson, Raymond P.; Schmalzer, David K.; Wright, Charles H.

    1982-12-21

    The relative ratio of heavy distillate to light distillate produced in a coal liquefaction process is continuously controlled by automatically and continuously controlling the ratio of heavy distillate to light distillate in a liquid solvent used to form the feed slurry to the coal liquefaction zone, and varying the weight ratio of heavy distillate to light distillate in the liquid solvent inversely with respect to the desired weight ratio of heavy distillate to light distillate in the distillate fuel oil product. The concentration of light distillate and heavy distillate in the liquid solvent is controlled by recycling predetermined amounts of light distillate and heavy distillate for admixture with feed coal to the process in accordance with the foregoing relationships.

  2. Shock-induced modification of a coal-derived pyrite. [Effects on liquefaction conversions

    SciTech Connect

    Morosin, B.; Stohl, F.V.; Graham, R.A.; Richards, P.; Granoff, B.; Williamson, D.L.

    1983-09-01

    Objectives were to characterize the effects of high-pressure shock-wave loadings on a coal-derived pyrite and to determine the effect of the increased defect concentration of the pyrite on coal liquefaction. The materials used were Robena pyrite with about 30 wt. % of phases other than FeS/sub 2/ and a sample of cleaned Robena pyrite which only contained pyrite and marcasite. The defect concentration in these materials was altered by the use of high-pressure shock-wave loadings with peak pressures of 10 to 15 GPa and peak temperatures of 600 to 900/sup 0/K. Both shocked materials showed broadened high 2THETA lines in the pyrite x-ray pattern which were caused by strain-induced lattice defects. The shocked uncleaned pyrite showed the presence of two additional phases, Fe/sub 3/C and pyrrhotite. The shocked cleaned pyrite showed the possible formation of smythite (Fe/sub 9/S/sub 11/) and pyrrhotite. Catalytic activity tests of the shocked cleaned pyrite were carried out in tubing reactors with West Virginia Blacksville No. 2 coal and SRC-II heavy distillate at 425/sup 0/C. The toluene and THF conversions from the runs with the shocked cleaned pyrite were similar to those obtained from the unshocked cleaned pyrite. This suggests that pyrite may not be the active phase which yields improvements in coal liquefaction or that the defects in pyrite are lost under coal-liquefaction conditions.

  3. Catalytic multi-stage liquefaction of coal at HTI: Bench-scale studies in coal/waste plastics coprocessing

    SciTech Connect

    Pradhan, V.R.; Lee, L.K.; Stalzer, R.H.

    1995-12-31

    The development of Catalytic Multi-Stage Liquefaction (CMSL) at HTI has focused on both bituminous and sub-bituminous coals using laboratory, bench and PDU scale operations. The crude oil equivalent cost of liquid fuels from coal has been curtailed to about $30 per barrel, thus achieving over 30% reduction in the price that was evaluated for the liquefaction technologies demonstrated in the late seventies and early eighties. Contrary to the common belief, the new generation of catalytic multistage coal liquefaction process is environmentally very benign and can produce clean, premium distillates with a very low (<10ppm) heteroatoms content. The HTI Staff has been involved over the years in process development and has made significant improvements in the CMSL processing of coals. A 24 month program (extended to September 30, 1995) to study novel concepts, using a continuous bench scale Catalytic Multi-Stage unit (30kg coal/day), has been initiated since December, 1992. This program consists of ten bench-scale operations supported by Laboratory Studies, Modelling, Process Simulation and Economic Assessments. The Catalytic Multi-Stage Liquefaction is a continuation of the second generation yields using a low/high temperature approach. This paper covers work performed between October 1994- August 1995, especially results obtained from the microautoclave support activities and the bench-scale operations for runs CMSL-08 and CMSL-09, during which, coal and the plastic components for municipal solid wastes (MSW) such as high density polyethylene (HDPE)m, polypropylene (PP), polystyrene (PS), and polythylene terphthlate (PET) were coprocessed.

  4. Non-catalytic liquefaction of coal with bagasse, a biomass waste

    SciTech Connect

    Rafiqul, I.; Lugang, B.; Yan, Y.; Li, T.

    1999-07-01

    Liquefaction of a Chinese bituminous coal with bagasse, a kind of biomass waste, have been carried out in an autoclave of 300 ml capacity at a temperature range of 350--450 C, reaction time 15--45 min and cool hydrogen pressure 300--700 PSIG (2.04 4.76 MPa). Optimization of the co-liquefaction process was done with respect to oil yield by Factorial Experiment Design Method. Oil yield reached 48% at optimum conditions of temperature: 420 C, cool hydrogen pressure: 500 PSIG and reaction time: 40 min. A polynomial mathematical model, a second order response surface model, has been obtained for correlating the oil yield response factor as well as conversion with the major process variables. The equation derived by the authors holds good in determining the effect of process variables on response factors for any regime conditions in the range of the Planned Experimental Design. Experimental data were also correlated by a kinetic model. The model is based on coal and bagasse, undergoing thermal cracking, is first converted parallel to form preasphaltene and asphaltene and low molecular gaseous products; then consecutively oil is formed from preasphaltene and asphaltene. Activation energies for these three reactions are 32.51 KJ/mol, 75.14 KJ/mol and 44.65 KJ/mol, respectively. These values are lower than that of liquefaction of coal alone. It justifies that the addition of bagasse is effective in enhancing the process of co-liquefaction and giving higher yield of oil than for liquefaction of coal alone. Calculated values from this model fairly agree with the experimental data.

  5. Coal liquefaction process streams characterization and evaluation:. Characterization of coal liquids by field ionization mass spectrometry and iodotrimethylsilane derivatization

    SciTech Connect

    Malhotra, R.; McMillen, D.F.; Burke, F.P.; Winschel, R.A.; Brandes, S.D.

    1992-01-01

    SRI International evaluated two analytical methods for application to coal liquefaction. These included field ionization mass spectrometry and a technique employing iodotrimethylsilane for the derivatization of oxygen bound to alkyl carbon (alkyl ethers). The full report authored by the SRI researchers is presented here. The following assessment briefly highlights the major findings of the project, and evaluates the potential of the methods for application to coal-derived materials. These results will be incorporated by Consol into a general overview of the application of novel analytical techniques to coal-derived materials at the conclusion of this contract. (VC)

  6. Mild acidic pretreatment to enhance low severity coal liquefaction promoted by cyclic olefins. Quarterly report, July 1995--September 1995

    SciTech Connect

    Curtis, C.W.

    1996-03-01

    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.

  7. "An Economic Process for Coal Liquefaction to Liquid Fuels" SBIR Phase II -- Final Scientific/Technical Report

    SciTech Connect

    Ganguli, Partha Sarathi

    2009-02-19

    The current commercial processes for direct coal liquefaction utilize expensive backmix-flow reactor system and conventional catalysts resulting in incomplete and retrogressive reactions that produce low distillate liquid yield and high gas yield, with high hydrogen consumption. The new process we have developed, which uses a less expensive reactor system and highly active special catalysts, resulted in high distillate liquid yield, low gas yield and low hydrogen consumption. The new reactor system using the special catalyst can be operated smoothly for direct catalytic coal liquefaction. Due to high hydrogenation and hydrocracking activities of the special catalysts, moderate temperatures and high residence time in each stage of the reactor system resulted in high distillate yield in the C{sub 4}-650{degrees}F range with no 650{degrees}F{sup +} product formed except for the remaining unconverted coal residue. The C{sub 4}-650{degrees}F distillate is more valuable than the light petroleum crude. Since there is no 650{degrees}F{sup +} liquid product, simple reforming and hydrotreating of the C{sub 4}-650{degrees}F product will produce the commercial grade light liquid fuels. There is no need for further refinement using catalytic cracking process that is currently used in petroleum refining. The special catalysts prepared and used in the experimental runs had surface area between 40-155 m{sup 2}/gm. The liquid distillate yield in the new process is >20 w% higher than that in the current commercial process. Coal conversion in the experimental runs was moderate, in the range of 88 - 94 w% maf-coal. Though coal conversion can be increased by adjustment in operating conditions, the purpose of limiting coal conversion to moderate amounts in the process was to use the remaining unconverted coal for hydrogen production by steam reforming. Hydrogen consumption was in the range of 4.0 - 6.0 w% maf-coal. A preliminary economic analysis of the new coal liquefaction process was

  8. Coal liquefaction in an inorganic-organic medium. [DOE patent application

    DOEpatents

    Vermeulen, T.; Grens, E.A. II; Holten, R.R.

    Improved process for liquefaction of coal by contacting pulverized coal in an inorganic-organic medium solvent system containing a ZnCl/sub 2/ catalyst, a polar solvent with the structure RX where X is one of the elements O, N, S, or P, and R is hydrogen or a lower hydrocarbon radical; the solvent system can contain a hydrogen donor solvent (and must when RX is water) which is immiscible in the ZnCl/sub 2/ and is a hydroaromatic hydrocarbon selected from tetralin, dihydrophenanthrene, dihydroanthracene or a hydrogenated coal derived hydroaromatic hydrocarbon distillate fraction.

  9. Advanced Direct Liquefaction Concepts for PETC Generic Units - Phase II

    SciTech Connect

    1997-12-01

    The results of Laboratory and Bench-Scale experiments and supporting technical and economic assessments conducted under DOE Contract No. DE-AC22-91PC91040 are reported for the period July 1, 1997 to September 30, 1997. This contract is with the University of Kentucky Research Foundation which supports work with the University of Kentucky Center for Applied Energy Research, CONSOL, Inc., LDP Associates, and Hydrocarbon Technologies, Inc. This work involves the introduction into the basic two stage liquefaction process several novel concepts which include dispersed lower-cost catalysts, coal cleaning by oil agglomeration, and distillate hydrotreating and dewaxing. Results are reported from experiments in which various methods were tested to activate dispersed Mo precursors. Several oxothiomolybdates precursors having S/Mo ratios from two to six were prepared. Another having a S/Mo ratio of eleven was also prepared that contained an excess of sulfur. In the catalyst screening test, none of these precursors exhibited an activity enhancement that might suggest that adding sulfur into the structure of the Mo precursors would be beneficial to the process. In another series of experiments, AHM impregnated coal slurried in the reaction mixture was pretreated withH S/H under pressure and successively heated for 30 min at 120, 250 2 2 and 360 C. THF conversions in the catalyst screening test were not affected while resid conversions o increased such that pretreated coals impregnated with 100 ppm Mo gave conversions equivalent to untreated coals impregnated with 300 ppm fresh Mo. Cobalt, nickel and potassium phosphomolybdates were prepared and tested as bimetallic precursors. The thermal stability of these compounds was evaluated in TG/MS to determine whether the presence of the added metal would stabilize the Keggin structure at reaction temperature. Coals impregnated with these salts showed the Ni and Co salts gave the same THF conversion as PMA while the Ni salt gave higher

  10. Two-stage, close coupled catalytic liquefaction of coal

    SciTech Connect

    Comolli, A.G.; Johanson, E.S.; Panvelker, S.V.; Popper, G.A.; Smith, T.O.

    1990-09-01

    During the first quarter of 1990, work was carried out in the microautoclave, microreactor, and Bench-Scale units. An economics analysis on sub-bituminous coal processing at two space velocities was also completed. Several supported catalysts and a sample of iron oxide were screened in the microautoclave unsulfided and sulfided with DMDS and TNPS. A second shipment of Black Thunder coal from Wilsonville, oil agglomerated cleaned Illinois {number sign}6 coal from Homer City, OTISCA cleaned coal a New Mexico coal were evaluated for relative conversions with and without catalyst. Results of Bench-Scale developments with cleaned, oil agglomerated, Illinois {number sign}6 coal from Homer City(CC-6), Dispersed Catalyst/Supported Catalyst Two-Stage and reversed sequential operation (CC-7), on Black Thunder Coal (CC-7), and preliminary observations on OTISCA cleaned coal are presented. The oil agglomerated cleaned coal gave higher conversion and distillate production than the OTISCA cleaned coal. The Dispersed/Supported Two-Stage operation yielded higher gas production than the reverse sequence but also showed the higher coal conversion. Economic analysis of sub-bituminous coal processing at two space velocities showed a 3% higher return on investment with a 50% increase in space velocity. 13 tabs.

  11. Catalytic coal liquefaction with treated solvent and SRC recycle

    DOEpatents

    Garg, Diwakar; Givens, Edwin N.; Schweighardt, Frank K.

    1986-01-01

    A process for the solvent refining of coal to distillable, pentane soluble products using a dephenolated and denitrogenated recycle solvent and a recycled, pentane-insoluble, solvent-refined coal material, which process provides enhanced oil-make in the conversion of coal.

  12. Coal liquefaction process using pretreatment with a binary solvent mixture

    DOEpatents

    Miller, Robert N.

    1986-01-01

    An improved process for thermal solvent refining or hydroliquefaction of non-anthracitic coal at elevated temperatures under hydrogen pressure in a hydrogen donor solvent comprises pretreating the coal with a binary mixture of an aromatic hydrocarbon and an aliphatic alcohol at a temperature below 300.degree. C. before the hydroliquefaction step. This treatment generally increases both conversion of coal and yields of oil.

  13. Catalytic coal liquefaction with treated solvent and SRC recycle

    DOEpatents

    Garg, D.; Givens, E.N.; Schweighardt, F.K.

    1986-12-09

    A process is described for the solvent refining of coal to distillable, pentane soluble products using a dephenolated and denitrogenated recycle solvent and a recycled, pentane-insoluble, solvent-refined coal material, which process provides enhanced oil-make in the conversion of coal. 2 figs.

  14. Process simulation model for indirect coal liquefaction using slurry reactor Fischer-Tropsch technology

    SciTech Connect

    Choi, G.N.; Tam, S.S.

    1994-12-31

    A detailed baseline design for indirect coal liquefaction using advanced Fischer-Tropsch (F-T) technology has been developed for Illinois No. 6 coal. This design forms the basis for an ASPEN process flowsheet simulation (PFS) model which can simulate the entire liquefaction plant and predict the effects of key process variables on the overall plant performance. A linear programming (I-P) model based on a typical PADD II refinery was developed for product valuation and a discounted cash flow (DCF) spreadsheet model was developed for economic analysis. These closely coupled models constitute a research tool which the DOE can use to plan, guide and evaluate its ongoing and future research programs for the manufacture of synthetic liquid fuels by indirect coal liquefaction. This paper covers the use of the ASPEN process simulation model and DCF spreadsheet model to look at the sensitivity of the economics to certain global process variables such as coal feed rate, synthesis gas conversion per pass and wax yield, together with certain specific reactor operating variables such as temperature, superficial velocity, slurry concentration, catalyst activity and catalyst life. Results are reported in terms of investment cost, yields and operating costs, which are then combined to determine a crude oil equivalent (COE) price. The COE is a hypothetical breakeven crude oil price at which a typical PADD II refinery could buy either crude oil or the coal liquefaction products. It is a present day value and is defined assuming constant deltas between crude oil and its products (i.e. constant refinery processing costs and margins).

  15. Decarboxylation of coal model compounds under liquefaction conditions: Does decarboxylation lead to retrograde reactions?

    SciTech Connect

    Eskay, T.P.; Britt, P.F.; Buchanan, A.C. III

    1996-12-31

    In recent years, it has become clear that oxygen functional groups in low-rank coals are major actors in retrograde reactions which inhibit their efficient thermochemical processing. In the pyrolysis and liquefaction of low-rank coals, low-temperature cross-linking reactions have been correlated with the loss of carboxyl groups and the evolution of CO{sub 2} and H{sub 2}O. Pretreatments such as methylation, demineralization, or ion-exchange of the inorganic cations reduce cross-linking and CO{sub 2} evolution in pyrolysis. Cross-linking reactions also have a deleterious effect on liquefaction yields and the distribution of oils, preasphaltenes and asphaltenes. These results suggest that decarboxylation may occur by a pathway that initiates retrograde (cross-linking) reactions in the coal polymer independent of the reaction conditions. However, the decarboxylation pathways in liquefaction and pyrolysis of low-rank coals are not known, and it is not clear how decarboxylation leads to cross-linking. Radical recombination or radical addition reactions have been suggested as being involved in retrograde reactions. However, the involvement of radical pathways in thermal decarboxylation reactions has recently been brought into question. We have presented evidence that in the pyrolysis of several bibenzyls containing aromatic carboxylic acids, radical pathways are not involved in thermal decarboxylation reactions and no cross-linking or coupling products are formed. Further, Manion et al. observed that decarboxylation of benzoic acid derivatives in tetralin yielded only small amounts of aryl-aryl coupling products. To gain a better understanding of the role decarboxylation plays in cross-linking reactions during liquefaction in low-rank coals, we have studied the thermal decomposition of several bibenzyls containing aromatic carboxylic acids, and their salts, in the presence of a hydrogen donor solvent (tetrahn) and a nondonor solvent (naphthalene).

  16. Coal liquefaction and hydrogenation: Processes and equipment. September 1971-November 1989 (A Bibliography from the US Patent data base). Report for September 1971-November 1989

    SciTech Connect

    Not Available

    1990-03-01

    This bibliography contains citations of selected patents concerning coal liquefaction and hydrogenation. Coal-liquefaction and -hydrogenation processes, catalysts and catalyst recovery, desulfurization, pretreatment of coals, energy recovery processes, solvent-product separation, and process variables are among the topics discussed. Liquefaction and hydrogenation processes include those employing catalysts such as manganese compounds, iron compounds, or chromium compounds; metal/iodine systems using different feedstocks such as coal solvent slurries, coke, extracted coals, distilled coals, or other pretreated coals; and systems using different hydrogenating gases such as methane or hydrogen. (Contains 253 citations fully indexed and including a title list.)

  17. Silylation of coal liquefaction products and an aid to phenol identification

    SciTech Connect

    Wolfson, A.C.; Farnum, S.A.; Miller, D.J.; Kongshaug, P.A.; Timpe, R.

    1984-01-01

    We have an ongoing program to identify phenols present in low-rank coal-derived liquids. We have developed a method for the conversion of the phenols to their trimethylsilyl ethers that facilitates the study of the phenols in liquefaction products. It has been reported that trimethylsilylation increases the volatility of phenols. This increase in volatility is very useful for gas chromatography (GC), permitting analysis of otherwise non-volatile phenols. An additional advantage of trimethylsilylation is that intermolecular hydrogen bonding of the phenols is diminished, thus reducing tailing on the gas chromatograms. Before attempting to silylate phenols in liquefaction products, we optimized the silylation conditions for a series of model compounds, which had previously been identified in our liquefaction products. Our liquefaction process yields three major liquid product types: a water fraction, a light oil, and a heavy oil. All three fractions have phenols present, but differ in the relative amounts of each type. The polar fraction of a pentane-soluble oil, obtained from silica gel column chromatography of a heavy oil, was silylated as shown in equation 1. Gas chromatographic analysis of the silylated product indicates an increase in volatility, as expected. The silylation appeared to be quantitative because there was no evidence of any underivatized phenols. We have found that trimethylsilylation of low-rank coal-derived liquids is a valuable addition to our present methods of phenol identification.

  18. Coal liquefaction catalyst development. Quarterly progress report No. 3, October 1-December 31, 1979

    SciTech Connect

    Kim, D. K.; Pellet, R. J.; Mahoney, J. A.

    1980-01-01

    Catalytic baseline runs continued with HDS-1442A in order to improve our baseline statistics as well as to monitor batch reactor performance. Testing of several new catalyst formulations was completed. No promising candidates for testing in the continuous aging unit were identified. The new SRC-II slurry oil was evaluated as a hydrogen donor liquefaction solvent. Our data indicates that the SRC-II heavy distillate oil is not as effective a hydrogen donor solvent as the hydrogenated anthracene oil. It is possible that the catalyst plays a key role in the thermal liquefaction reactions by improving the hydrogen donor properties of the slurry oil through in-situ hydrogenation. The differences in liquefaction behavior between Illinois No. 6 and Wyodak coal were determined. A major portion of our effort was concerned with ascertaining the liquefaction behavior of a Western coal such as Wyodak with AMOCAT type catalysts. A two-month program to determine the feasibility of using the Amoco continuous aging unit for SRC-I product upgrading was outlined.

  19. Non-catalytic transfer hydrogenation in supercritical CO2 for coal liquefaction

    NASA Astrophysics Data System (ADS)

    Elhussien, Hussien

    This thesis presents the results of the investigation on developing and evaluating a low temperature (<150°C) non - catalytic process using a hydrogen transfer agent (instead of molecu-lar hydrogen) for coal dissolution in supercritical CO2. The main idea behind the thesis was that one hydrogen atom from water and one hydrogen atom from the hydrogen transfer agent (HTA) were used to hydrogenate the coal. The products of coal dissolution were non-polar and polar while the supercritical CO2, which enhanced the rates of hydrogenation and dissolution of the non-polar molecules and removal from the reaction site, was non-polar. The polar modifier (PM) for CO2 was added to the freed to aid in the dissolution and removal of the polar components. The addition of a phase transfer agent (PTA) allowed a seamless transport of the ions and by-product between the aqueous and organic phases. DDAB, used as the PTA, is an effective phase transfer catalyst and showed enhancement to the coal dissolution process. COAL + DH- +H 2O → COAL.H2 + DHO-- This process has a great feature due to the fact that the chemicals were obtained without requir-ing to first convert coal to CO and H2 units as in indirect coal liquefaction. The experiments were conducted in a unique reactor set up that can be connected through two lines. one line to feed the reactor with supercritical CO 2 and the other connected to gas chromatograph. The use of the supercritical CO2 enhanced the solvent option due to the chemical extraction, in addition to the low environmental impact and energy cost. In this thesis the experiment were conducted at five different temperatures from atmos-pheric to 140°C, 3000 - 6000 psi with five component of feed mixture, namely water, HTA, PTA, coal, and PM in semi batch vessels reactor system with a volume of 100 mL. The results show that the chemicals were obtained without requiring to first convert coal to CO and H2 units as in indirect coal liquefaction. The results show that

  20. Design, synthesis, and characterization of novel fine-particle, unsupported catalysts for coal liquefaction. Technical progress report, October 25, 1990--October 24, 1991: Draft

    SciTech Connect

    Klein, M.T.

    1991-12-30

    The purpose of this work is to investigate the kinetics-assisted design, synthesis and characterization of fme-pardcle, unsupported catalysts for coal liquefaction. The goal is to develop a fundamental understanding of coal catalysis and catalysts that will, in turn, allow for the specification of a novel optimal catalyst for coal liquefaction.

  1. Design, synthesis, and characterization of novel fine-particle, unsupported catalysts for coal liquefaction. Technical progress report, October 26, 1991--January 25, 1992: Draft

    SciTech Connect

    Klein, M.T.; Foley, H.C.

    1992-03-23

    The purpose of this work is to investigate the kinetics-assisted design, synthesis and characterization of fine-particle, unsupported catalysts for coal liquefaction. The goal is to develop a fundamental understanding of coal catalysis and catalysts that will, in turn, allow for the specification of a novel optical catalyst for coal liquefaction.

  2. Fundamental studies of coal liquefaction. Quarterly report No. 7, April 1--July 1, 1993

    SciTech Connect

    Ross, D.S.

    1993-07-14

    In our last report we discussed observations in our cell concerning the behavior or Illinois No. 6 coal in tetralin to 460{degrees}C. We noted that there were possibly two distinct types of particles comprising the organic phase, reacting respectively at 420{degrees}--430{degrees}C, and at 450{degrees}--460{degrees}C. Alternatively we could interpret the data as describing a range of reactivity bounded by those temperatures. As evidenced by the contraction of the particles, the reactions were rapid. The particles lost half of their substance within 1 min, and we suggested that the rates were too fast to be accommodated by the commonly held scheme for coal liquefaction involving thermolytic scission of weak, bibenzyl-like bonds. Our analyses were aided by our use of Adobe Photoshop, which allows us to store, digitized versions of our recorded images. The images can then be manipulated at will to provide quantitative data on morphological changes. We noted in our last report that printer limitations prevented us from presenting images with the desirable quality, and we are at present attempting to find access to equipment which will provide satisfactory figures. Accordingly our progress will be described here without any photographs, and we expect to present a more complete account of our work in our next report. The work reported here includes studies of Illinois No. 6 coal with water as the medium, and a control run with argon as medium. Our temperature ramping was like that used last time, 25{degrees}C/min to 250{degrees}C, and then 10{degrees}C/min to 450{degrees}C. The results from the earlier work and the data presented here can therefore be directly compared.

  3. Microbial recovery of metals from spent coal liquefaction catalysts. Quarterly report, October--December 1991

    SciTech Connect

    Sperl, P.L.; Sperl, G.T.

    1991-12-31

    This project was initiated on October 1, 1989, for the purpose of recovering metals from spent coal liquefaction catalysts. The catalyst is a Ni-Mo catalyst supported on alumina (Shell 324) as is used in a pilot scale coal liquefaction facility at Wilsonville, Alabama. This plant is run and operated by Southern Clean Fuels. A large sample of spent catalyst from this facility has been obtained. The object of the contract is to treat the spent catalysts with microorganisms, especially Thiobacillus ferrooxidans, but also other Thiobacillus sp. and possibly Sulfolobus, and other potentially useful microorganisms to leach and remove the metals (Ni and Mo) form the spent catalysts into a form which can be readily recovered by conventional techniques.

  4. Microbial recovery of metals from spent coal liquefaction catalysts. [Thiobacillus denitrificans, Sulfolobus

    SciTech Connect

    Sperl, P.L.; Sperl, G.T.

    1991-01-01

    This project was initiated on October 1, 1989, for the purpose of recovering metals from spent coal liquefaction catalysts. The catalyst is a Ni-Mo catalyst supported on alumina (Shell 324) as is used in a pilot scale coal liquefaction facility at Wilsonville, Alabama. This plant is run and operated by Southern Clean Fuels. A large sample of spent catalyst from this facility has been obtained. The object of the contract is to treat the spent catalysts with microorganisms, especially Thiobacillus ferrooxidans, but also other Thiobacillus sp. and possibly Sulfolobus, and other potentially useful microorganisms to leach and remove the metals (Ni and Mo) form the spent catalysts into a form which can be readily recovered by conventional techniques.

  5. Steam pretreatment for coal liquefaction. [Monthly report], September 1, 1993--September 30, 1993

    SciTech Connect

    1993-10-10

    Rapid heating liquefaction of steam pretreated Illinois No.6 coal mixed with 4A zeolite was carried out this month. Liquefaction yields are close to those obtained with 5A zeolite at the same coal/zeolite ration. Aquathermolysis of model compound 9-phenoxyphenanthrene was carried out this month under conditions similar to employed by Katritzky but for shorter time. Analysis of recovered products showed incomplete cleavage of the ether. This demonstrates the importance of longer reaction time even at high pressure. It will be of interest to determine if high conversions can be achieved at long reaction times and low pressure. Additional amounts of model compounds 2-naphthyl methyl phenyl ether and 2-naphthyl benzyl ether were synthesized. Purification of these compounds are now in progress.

  6. Anaerobic liquefaction/solubilization of coal by microorganisms and isolated enzymes

    SciTech Connect

    Scott, C.D.; Faison, B.D.; Woodward, C.A.

    1991-01-01

    Biocatalytic systems utilizing either living organisms or modified enzymes have been shown to enhance the liquefaction (products are liquid at ambient conditions) or solubilization of coal under anaerobic conditions. Microbial tests have been carried out in aqueous media with organisms isolated from outcropping of coal or from premium coal samples. Some of these isolates have been shown to grow on coal as the only carbon source and to produce small quantities of oxychemicals such as acetate or ethanol. Reducing enzymes, such as hydrogenase and cytochrome C, can be chemically modified to increase solubilization in organic solvents by attaching less polar chemicals, such as phenyl groups or polyethylene glycol, to the free amino groups on the enzymes. These biocatalysts have been shown to degrade model compounds and enhance the solubilization of coal in organic solvents under a hydrogen atmosphere. The resulting product is a relatively light hydrocarbon mixture with reasonably high volatility. 5 refs., 6 figs., 4 tabs.

  7. Catalytic coal liquefaction. Quarterly report, April-June 1982. [Ammonium paramolybdate; stannous chloride

    SciTech Connect

    Weller, S.W.

    1982-01-01

    Coal liquefaction experiments have been carried out in a stirred autoclave under nitrogen. Tetralin was employed as solvent, and the catalyst, when used, was ammonium paramolybdate (impregnated) or stannous chloride (powdered). Production of pentane-soluble oil was higher in the runs with catalysts, but the net hydrogen transfer from tetralin to coal was less when catalyst was used. Coal and powdered stannous chloride exhibited a marked synergistic effect on the dehydrogenation of tetralin. A free radical mechanism was suggested to explain this effect, and model experiments with bibenzyl (but no coal) gave results that were consistent with this mechanism. An apparent synergistic effect of coal and impregnated ammonium paramolybdate was shown to be attributable simply to improved distribution (higher surface area) of the impregnated catalyst.

  8. Continuous bench-scale slurry catalyst testing: Direct coal liquification of Rawhide sub-bituminous coal. Technical report, July 1995--December 1995

    SciTech Connect

    Coless, L.A.; Poole, M.C.; Wen, M.Y.

    1996-05-24

    In 1994 extensive tests were conducted in the Exxon Research and Engineering Recycle Coal Liquefaction Unit (RCLU) in Baton Rouge, Louisiana. The work conducted in 1994 explored a variety of dispersed iron molybdenum promoted catalyst systems for direct coal liquefaction of Rawhide subbituminus coal. The goal was to identify the preferred iron system. We learned that among the catalysts tested, all were effective; however, none showed a large process advantage over the others. In 1995, we tested dispersed molybdenum catalysts systems for direct coal liquefaction on a second subbituminous coal, Black Thunder. Catalyst properties are shown in Table 1. We also checked a molybdenum promoted iron case, as well as the impact of process variables, such as sulfur type, hydrogen treat rate, and catalyst addition rate, as shown in Table 2. In 1995, we ran 18 material balances over a 7 week period, covering 7 conditions. This report covers the 1995 operations and results.

  9. General quantitative model for coal liquefaction kinetics: the thermal cleavage/hydrogen donor capping mechanism. [59 references

    SciTech Connect

    Gangwer, T

    1980-01-01

    A mechanism for coal liquefaction, based on the concept of thermal cleavage-hydrogen capping donor complexes, is proposed and the quantitative agreement between the derived rate laws and the kinetic data obtained from fifteen publications is presented. The mechanism provides rate laws which describe the preasphaltene, asphaltene, oil and gas time/yield curves for the coal liquefaction process. A simplistic dissolution model is presented and used to relate the proposed mechanism to the experimentally observed products. Based on the quality of the mechanistic fit to the reported coal liquefaction systems, which cover a diverse range of reaction conditions, coal types and donor solvent compositions, it is proposed that the donor solvent/thermal bond cleavage/hydrogen capping mechanism provides a good, quantitative description of the rate limiting process. Interpretation of the rate constant/temperature dependencies in terms of transition state theory indicates formation of the activated complex can involve either physically or chemically controlled steps. A uniform free energy of activation of 52 kcal was found for the diverse liquefaction systems indicating a common transition state describes the reactions. Thus the proposed mechanism unifies the diverse liquefaction kinetic data by using a set of uniform reaction sequences, which have a common transition state, to describe the conversion chemistry. The mechanism thereby creates a common base for intercomparison, interpretation and evaluation of coal conversion for the broad range of processes currently being investigated in the liquefaction field.

  10. Coal liquefaction process using pretreatment with a binary solvent mixture

    DOEpatents

    Miller, R.N.

    1986-10-14

    An improved process for thermal solvent refining or hydroliquefaction of non-anthracitic coal at elevated temperatures under hydrogen pressure in a hydrogen donor solvent comprises pretreating the coal with a binary mixture of an aromatic hydrocarbon and an aliphatic alcohol at a temperature below 300 C before the hydroliquefaction step. This treatment generally increases both conversion of coal and yields of oil. 1 fig.

  11. Corrosion studies at the Wilsonville, Alabama, coal liquefaction facility during 1983

    SciTech Connect

    Keiser, J.R.; Olsen, A.R.; Newsome, J.F.; Howell, M.

    1984-10-01

    During 1983, Oak Ridge National Laboratory continued a study of materials performance at the Wilsonville, Alabama, Advanced Coal Liquefaction Research and Development Facility. Materials performance was evaluated by exposure and analysis of corrosion coupons and U-bend specimens, chemical analysis of related process streams, and ultrasonic determination of the thickness of walls of various components. The results of these studies are useful to current plant operators and to designers of future large-scale plants. 18 references, 4 figures, 12 tables.

  12. Potential terrestrial fate and effects on soil biota of a coal liquefaction product spill

    SciTech Connect

    Strayer, R.F.; Edwards, N.T.; Walton, B.T.; Charles-Shannon, V.

    1983-01-01

    Contaminated soil samples collected from the site of a coal liquefaction product spill were used to study potential fates and effects of this synthetic fuel. Simulated weathering in the laboratory caused significant changes in residual oil composition. Soil column leachates contained high phenol levels that decreased exponentially over time. Toxicity tests demonstrated that the oil-contaminated soil was phytotoxic and caused embryotoxic and teratogenic effects on eggs of the cricket Acheta domesticus.

  13. Effects of the components of coal hydro-liquefaction residue on its rheological characteristics

    SciTech Connect

    Ren, Y.; Jin, S.; Xu, Y.; Wei, A.; Zhang, D.; Gao, J.

    2009-07-01

    Four kinds of typical coal liquefaction residue samples, coming from Shenhua coal liquefaction pilot plant, were used to investigate the effects of components of residue, separation time, and temperature on its rheological characteristics. Coal liquefaction residue is a non-Newtonian pseudoplastic fluid whose apparent viscosity decreases with increasing shear rate. Moreover, the residue has high viscosity at the initial softening temperature, and its viscosity drops greatly with increasing temperature. The oil content in residue has a great effect on the decline of the apparent viscosity of residue. The asphaltene can increase the apparent viscosity at lower temperatures but decrease it at higher temperatures. However, the solid only increases the apparent viscosity as it can be neither softened nor dissolved to become fluid. After simulating the separation condition, it is found that prolonging the separation time and enhancing the separation temperature will increase the apparent viscosity of residue, which is bad for preventing pipes from being blocked. So choosing the right separation time and separation temperature is necessary to actual industrial production.

  14. Liquefaction and desulfurization of coal using synthesis gas

    DOEpatents

    Fu, Yuan C.

    1977-03-08

    A process for desulfurizing and liquefying coal by heating said coal at a temperature of 375.degree.-475.degree. C in the presence of a slurry liquid, hydrogen, carbon monoxide, steam, and a catalyst comprising a desulfurization catalyst and an alkali metal salt.

  15. Multi-stage coal liquefaction and fractionation method

    SciTech Connect

    Gir, S.; Rhodes, D.E.

    1987-05-12

    A method is described of liquefying and fractionating coal comprising: mixing coal with a primary heavy solvent to form a coal-primary heavy solvent slurry; treating the coal-primary heavy solvent slurry under coal-liquefying conditions to form a primary feed solution; introducing at least a portion of the primary feed solution into a first primary separation zone to form a first light primary phase and a first heavy primary phase, separated by a liquid-liquid interface; and processing the separated first light primary phase in at least one primary separation zone successive to the first primary separation zone to separate, in a final successive primary separation zone, a final light primary phase and a final heavy primary phase.

  16. Novel nanodispersed coal liquefaction catalysts: Molecular design via microemulsion-based synthesis

    SciTech Connect

    Osseo-Asare, K.; Boakye, E.; Vaidyanathan, N.; Radovic, L.R.

    1992-04-01

    The objective of this project is to pursue the development of highly dispersed and inexpensive catalysts for improved coal solubilization and upgrading of coal liquids. A novel study of the synthesis of liquefaction catalysts of nanometer size will be carried out. It is based on the molecular design of reverse micelles (microemulsions). These surfactant-stabilized, metal-bearing microdrops offer unique opportunities for synthesizing very small particles by providing a cage-like effect that limits particle nucleation, growth and agglomeration. The emphasis will be on iron- and molybdenum-based catalysts, but the techniques to be developed should also be generally applicable. (VC)

  17. Novel nanodispersed coal liquefaction catalysts: Molecular design via microemulsion-based synthesis

    SciTech Connect

    Osseo-Asare, K.; Radovic, L.R.

    1991-07-01

    The objective of this project is to pursue the development of highly dispersed and inexpensive catalysts for improved coal solubilization and upgrading of coal liquids. A novel study of the synthesis of liquefaction catalysts of nanometer size will be carried out. It is based on the molecular design of reverse micelles (microemulsions). These surfactant-stabilized, metal-bearing microdrops offer unique opportunities for synthesizing very small particles by providing a cage-like effect that limits particle nucleation, growth and agglomeration. The emphasis will be on iron- and molybdenum-based catalysts, but the techniques to be developed should also be generally applicable. (VC)

  18. Novel nanodispersed coal liquefaction catalysts: Molecular design via microemulsion-based synthesis

    SciTech Connect

    Osseo-Asare, K.; Radovic, L.R.

    1991-02-01

    The objective of this project is to pursue the development of highly dispersed and inexpensive catalysts for improved coal solubilization and upgrading of coal liquids. A novel study of the synthesis of liquefaction catalysts of nanometer size will be carried out. It is based on the molecular design of reverse micelles (microemulsions). These surfactant-stabilized, metal-bearing microdrops offer unique opportunities for synthesizing very small particles by providing a cage-like effects that limits particle nucleation, growth and agglomeration. The emphasis will be on iron- and molybdenum-based catalysts, but the techniques to be developed should also be generally applicable.

  19. Fischer-Tropsch indirect coal liquefaction design/economics-mild hydrocracking vs. fluid catalytic cracking

    SciTech Connect

    Choi, G.N.; Kramer, S.J.; Tam, S.S.; Reagan, W.J.

    1996-12-31

    In order to evaluate the economics of Fischer-Tropsch (F-T) indirect coal liquefaction, conceptual plant designs and detailed cost estimates were developed for plants producing environmentally acceptable, high-quality, liquid transportation fuels meeting the Clean Air Act requirements. The designs incorporate the latest developments in coal gasification technology and advanced (F-T) slurry reactor design. In addition, an ASPEN Plus process simulation model was developed to predict plant material and energy balances, utility requirements, operating and capital costs at varying design conditions. This paper compares mild hydrocracking and fluid catalytic cracking as alternative methods for upgrading the F-T wax.

  20. Advanced direct liquefaction concepts for PETC generic units. Quarterly technical progress report, October 1992--December 1992

    SciTech Connect

    Not Available

    1993-02-01

    The reactivity of the THF insoluble fraction of the ashy resid component of Wilsonville recycle oil (WRO) during liquefaction of Black Thunder coal in tetralin was determined at 415{degrees}C and 60 minutes. The liquefaction runs were made by combining this material with Black Thunder coal at the same ratio used in the WRO coal runs. THF conversion and product distribution from liquefaction in tetralin in the presence of the THF insoluble fraction of the ashy resid were similar to results from liquefaction in WRO. THF conversion was greater than loot with an oil yield that was somewhat higher than in WRO. Differences in HC gas yield and H{sub 2} consumption were slight, while conversion and product distribution from liquefaction of Black Thunder coal in tetralin or in the WRO distillate were quite different. In both these solvents the 85--86% THF conversions were less than for runs in which the THF insoluble fraction of the ashy resid was present. This establishes that the THF insoluble fraction of the ashy resid is the reactive fraction of the WRO.

  1. Studies of the effect of selected nondonor solvents on coal liquefaction yields

    SciTech Connect

    Jolley, R. L.; Rodgers, B. R.; Benjamin, B. M.; Poutsma, M. L.; Douglas, E. C.; McWhirter, D. A.

    1983-09-01

    The objective of this research program was to evaluate the effectiveness of selected nondonor solvents (i.e., solvents that are not generally considered to have hydrogen available for hydrogenolysis reactions) for the solubilization of coals. Principal criteria for selection of candidate solvents were that the compound should be representative of a major chemical class, should be present in reasonable concentration in coal liquid products, and should have the potential to participate in hydrogen redistribution reactions. Naphthalene, phenanthrene, pyrene, carbazole, phenanthridine, quinoline, 1-naphthol, and diphenyl ether were evaluated to determine their effect on coal liquefaction yields and were compared with phenol and two high-quality process solvents, Wilsonville SRC-I recycle solvent and Lummus ITSL heavy oil solvent. The high conversion efficacy of 1-naphthol may be attributed to its condensation to binaphthol and the consequent availability of hydrogen. The effectiveness of both the nitrogen heterocycles and the polycyclic aromatic hydrocarbon (PAH) compounds may be due to their polycyclic aromatic nature (i.e., possible hydrogen shuttling or transfer agents) and their physical solvent properties. The relative effectiveness for coal conversion of the Lummus ITSL heavy oil solvent as compared with the Wilsonville SRC-I process solvent may be attributed to the much higher concentration of 3-, 4-, and 5-ring PAH and hydroaromatic constituents in Lummus solvent. The chemistry of coal liquefaction and the development of recycle, hydrogen donor, and nondonor solvents are reviewed. The experimental methodology for tubing-bomb tests is outlined, and experimental problem areas are discussed.

  2. Indirect liquefaction of coal. [Coal gasification plus Fischer-Tropsch, methanol or Mobil M-gasoline process

    SciTech Connect

    1980-06-30

    The most important potential environmental problems uniquely associated with indirect liquefaction appear to be related to the protection of occupational personnel from the toxic and carcinogenic properties of process and waste stream constituents, the potential public health risks from process products, by-products and emissions and the management of potentially hazardous solid wastes. The seriousness of these potential problems is related partially to the severity of potential effects (i.e., human mortality and morbidity), but even more to the uncertainty regarding: (1) the probable chemical characteristics and quantities of process and waste streams; and (2) the effectiveness and efficiencies of control technologies not yet tested on a commercial scale. Based upon current information, it is highly improbable that these potential problems will actually be manifested or pose serious constraints to the development of indirect liquefaction technologies, although their potential severity warrants continued research and evaluation. The siting of indirect liquefaction facilities may be significantly affected by existing federal, state and local regulatory requirements. The possibility of future changes in environmental regulations also represents an area of uncertainty that may develop into constraints for the deployment of indirect liquefaction processes. Out of 20 environmental issues identified as likely candidates for future regulatory action, 13 were reported to have the potential to impact significantly the commercialization of coal synfuel technologies. These issues are listed.

  3. Cooperative research in coal liquefaction. Final report, May 1, 1992--April 30, 1993

    SciTech Connect

    Huffman, G.P.

    1996-03-01

    Research on sulfate and metal (Mo, Sn) promoted Fe{sub 2}O{sub 3} catalysts in the current year focused on optimization of conditions. Parameters varied included temperature, solvent, solvent-to-coal ratio, and the effect of presulfiding versus in situ sulfiding. Oil yields were found to increase approximately proportionately with both temperature and solvent-to-coal ratio. The donor solvent, tetralin, proved to give better total conversion and oil yields than either 1-methylnaphthalene or Wilsonville recycle oil. A significant enhancement of both total liquefaction yields and oil yields from lignites and subbituminous coals has been achieved by incorporating iron into the coal matrix by cation exchange. A study has been conducted on the synthesis of iron, molybdenum, and tungsten catalysts using a laser pyrolysis technique.

  4. Fundamental Kinetics of Supercritical Coal Liquefaction: Effect of Catalysts and Hydrogen-Donor Solvents

    SciTech Connect

    McCoy, Ben J; Madras, Girodhar; Smith, J M; Kodera, Yoichi

    1997-04-16

    This is the quarterly report on our recent progress toward the overall objective to understand the supercritical fluid extraction of hydrocarbons from coal. Our strategy is to simulate coal as a high molecular-weight polymeric material by studying the degradation of polymers under various conditions. The hypothesis we are testing is that degradation of such macromolecules is applicable to the decomposition (depolymerization) of the coal network. Polymer degradation and coal liquefaction are influenced strongly by the solvent in the reaction. This motivated our investigation of the effect of hydrogen donor solvents on polymer degradation. In particular, we obtained new experimental data to show how a hydrogen donor, 6-hydroxy tetralin, influences the degradation rate of polystyrene. We also developed a detailed radical mechanism for hydrogen donation based on the Rice-Herzfeld chain reaction concept with the elementary steps of initiation, depropagation, hydrogen abstraction, and termination. Expressions for the degradation rate parameters were obtained by applying continuous distribution kinetics to the MWD of the reacting polymer. The theory explains the different influences of the hydrogen donor solvent on the degradation rate coefficients for different polymers. Though developed for the degradation of polymers, the mechanism and the theory are potentially applicable for chain scission and addition reactions among distributions of paraffins, olefins, and radicals of all chain lengths. The concepts can, in principle, be extended to examine the effect of hydrogen donors on coal liquefaction and on the complex mixture of liquefaction compounds. Based on this work, a research paper titled "Effect of Hydrogen Donors on Polymer Degradation", has been submitted for publication. Our research paper entitled, "Molecular weight effect on the dynamics of polystyrene degradation", has been accepted for publication by the journal, Industrial and Engineering Chemistry Research.

  5. Release of inorganic material during coal devolatilization

    SciTech Connect

    Baxter, L.L.; Mitchell, R.E.; Fletcher, T.H.

    1997-03-01

    Experimental results presented in this paper indicate that coal devolatilization products convectively remove a fraction of the nonvolatile components of inorganic material atomically dispersed in the coal matrix. Results from three facilities burning six different coals illustrate this mechanism of ash transformation and release from coal particles. Titanium is chosen to illustrate this mechanism of ash transformation and release from coal particles. Titanium is chosen to illustrate this type of mass release from coal particles on the basis of its low volatility and mode of occurrence in the coal. During moderate rates of devolatilization (10{sup 4} K/s heating rate), no significant loss of titanium is noted. At more rapid rates of heating/devolatilization (10{sup 5} K/s) a consistent but minot (3%--4%) loss of titanium is noted. During rapid devolatilization (5 {times} 10{sup 5} K/s and higher), significant (10%--20%) amounts of titanium leave the coal. The loss of titanium monitored in coals ranging in rank from subbituminous to high-volatile bituminous coals and under conditions typical of pulverized-coal combustion. The amount of titanium lost during devolatilization exhibits a complex rank dependence. These results imply that other atomically dispersed material (alkali and alkaline earth elements) may undergo similar mechanisms of transformation and release.

  6. (Pittsburgh Energy Technology Center): Quarterly technical progress report for the period ending June 30, 1987. [Advanced Coal Research and Technology Development Programs

    SciTech Connect

    1988-02-01

    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)

  7. DIRECT LIQUEFACTION PROOF-OF-CONCEPT PROGRAM - BENCH RUN PB-10 (HTI 227-109)

    SciTech Connect

    Unknown

    1999-12-30

    This report presents the results of the bench-scale test, PB-10, performed at HTI's facilities under DOE contract (HTI Run No. 227-109). This bench test continues the work that was started in PDU testing 260-007. Previous bench test (PB-09, HTI 227-106) was performed on different seams of Chinese coal (Shenhua Ningtiaota Coal No.2 and No.3). Since another coal, Shangwan coal was selected for the liquefaction plant, PB-10 was made as approved by DOE/COR. The objective of this test was to evaluate the liquefaction performance of Shangwan coal utilizing various backend processing and recycle schemes. Additionally, this test was to collect available process data to allow for the best scale-up process design possible from this particular unit.

  8. Novel nanodispersed coal liquefaction catalysts: Molecular design via microemulsion-based synthesis. Final technical report, October 1990--December 1994

    SciTech Connect

    Osseo-Asare, K.; Boakye, E.; Vittal, M.

    1995-04-01

    This report described the synthesis of Molybdenum Sulfides in microemulsions by acidification of ammonium tetrathiomolybdate. Molybdenum Sulfides have been shown to be potential coal liquefaction catalysts. The importance of particle size, temperature effects, and coal surface chemistry to impregnation are discussed.

  9. Novel bimetallic dispersed catalysts for temperature-programmed coal liquefaction. Technical progress report, October--December 1992

    SciTech Connect

    Song, Chunshan; Schobert, H.H.

    1993-02-01

    Development of new catalysts is a promising approach to more efficient coal liquefaction. It has been recognized that catalysts are superior to supported catalysts for primary liquefaction of coals, because the control of initial coal dissolution or depolymerization requires intimate contact between the catalyst and coal. This research is a fundamental and exploratory study on catalytic coal liquefaction, with the emphasis on the development of novel bimetallic dispersed catalysts for temperature-programmed liquefaction. The ultimate goal of the present research is to develop novel catalytic hydroliquefaction process using highly active dispersed catalysts. The primary objective of this research is to develop novel bimetallic dispersed catalysts from organometallic molecular that can be used in low precursors concentrations (< 1 %) but exhibit high activity for efficient hydroliquefaction of coals under temperature-programmed conditions. The major technical approaches are, first, to prepare the desired heteronuclear organometallic molecules as catalyst precursors that contain covalently bound, two different metal atoms and sulfur in a single molecule. Such precursors will generate finely dispersed bimetallic catalysts such as Fe-Mo, Co-Mo and Ni-Mo binary sulfides upon thermal decomposition. The second major technical approach is to perform the liquefaction of coals unpregnated with the organometallic precursors under temperature-programmed conditions, where the programmed heat-up serves as a step for both catalyst activation and coal pretreatment or preconversion. Two to three different complexes for each of the Fe-Mo, Co-Mo, and Ni-Mo combinations will be prepared. Initial catalyst screening tests will be conducted using a subbituminous coal and a bituminous coal. Effects of coal rank and solvents will be examined with the selected bimetallic catalysts which showed much higher activity than the dispersed catalysts from conventional precursors.

  10. Advanced Coal Liquefaction Research and Development Facility, Wilsonville, Alabama. Run 262 with Black Thunder subbituminous coal: Technical progress report

    SciTech Connect

    Not Available

    1992-09-01

    This report presents the results of Run 262 performed at the Advanced Coal Liquefaction R&D Facility in Wilsonville, Alabama. The run started on July 10, 1991 and continued until September 30, 1991, operating in the Close-Coupled Integrated Two-Stage Liquefaction mode processing Black Thunder Mine subbituminous coal (Wyodak-Anderson seam from Wyoming Powder River Basin). A dispersed molybdenum catalyst was evaluated for its performance. The effect of the dispersed catalyst on eliminating solids buildup was also evaluated. Half volume reactors were used with supported Criterion 324 1/16`` catalyst in the second stage at a catalyst replacement rate of 3 lb/ton of MF coal. The hybrid dispersed plus supported catalyst system was tested for the effect of space velocity, second stage temperature, and molybdenum concentration. The supported catalyst was removed from the second stage for one test period to see the performance of slurry reactors. Iron oxide was used as slurry catalyst at a rate of 2 wt % MF coal throughout the run (dimethyl disulfide (DMDS) was used as the sulfiding agent). The close-coupled reactor unit was on-stream for 1271.2 hours for an on-stream factor of 89.8% and the ROSE-SR unit was on-feed for 1101.6 hours for an on-stream factor of 90.3% for the entire run.

  11. Effect of coal liquefaction conditions on the composition of the product oil

    SciTech Connect

    Karaca, H.

    2006-12-15

    Two methods, catalyst physically mixing method (method I) and catalyst impregnation method (method II) were employed for Beypazari and Tuncbilek lignites liquefaction. Fe{sub 2}O{sub 3} and Mo(CO){sub 6} were used as the catalysts. Oils obtained at the end of the catalytic coal liquefaction were qualitatively analyzed by gas chromatography (GC). With solvent/coal ratio increase, compounds with straight chain and high molecular weight were formed. Likewise, as the reaction time and catalyst concentration were increased, the number and the intensity of the compounds in the oils increased partially. Due to the increase in the reaction time, temperature and catalyst concentration, the oils were enriched in straight chain alkanes and aromatic polycyclic compounds. However, alkanes with straight chain were reduced by the effect of pyrolysis at temperatures over 400{sup o}C. Retention times of the compounds obtained by method II were higher than those of the compounds obtained by method I. Respectively, the compounds in the oils obtained by method II were found to have been composed by high quantities of high molecular straight chain alkanes and aromatic polycyclic compounds. Our data gave us ground to presume that the oils from both lignites were composed by straight chain alkanes and aromatic polycyclic compounds (tetralin, naphthalene and their derivatives, phenols, xylenols, biphenyl, naphthols, etc.). The oil compositions were strongly influenced by the liquefaction conditions.

  12. Steam pretreatment for coal liquefaction. Fourth quarterly report, 1 July 1991--30 September 1991

    SciTech Connect

    Graff, R.A.; Balogh-Nair, V.

    1992-06-18

    Steam pretreatment is the reaction of coal with steam at temperatures well below those usually used for solubilization. The objective of the proposed work is to test the application of steam pretreatment to coal liquefaction. A 300 ml stirred autoclave for liquefaction tests is being installed. Pretreatment and extraction tests were made with Blind Canyon coal alone, mixed with Illinois No. 6 coal, impregnated with iron, and impregnated with iron and sulfided using phenyl disulfide. Measurements show an increase in volatiles yield and a decrease in extraction yield with catalyst addition. These results are not yet definitive, because both yields may be artificially decreased by insoluble residue from phenyl disulfide. About one ram of purified {alpha}-naphthylmethyl phenyl ether was prepared and an additional 0. 8 gram were synthesized. Steam pretreatment of the model compound {alpha}-benzylnaphthyl ether was repeated with a Pyrex liner for the reactor tube. No differences have yet appeared as a result of using this liner (compared to bare stainless steel), evidence against any catalytic wall effect.

  13. Low severity coal liquefaction promoted by cyclic olefins. Quarterly report, April--June 1992

    SciTech Connect

    Curtis, C.W.

    1992-07-27

    Low severity coal liquefaction allows for solubilization of coal with reduced gas make. These lower severity conditions may result in some selective bond rupture. Promotion of coal solubilization through hydrogen transfer using highly active and effective hydrogen donors is the objective of this study. The highly effective donors being tested are cyclic olefins. Representative cyclic olefins are isotetralin, which is 1,4,5,8-tetrahydronaphthalene, and 1,4,5,8,9,10-hexahydroanthracene. These compounds are hydroaromatics without aromatic rings and have been shown to be highly effective donors. The objective of the work performed in this study during this quarter was to evaluate reaction parameters for low severity liquefaction reactions using the cyclic olefin, hexahydroanthracene, and the aromatic, anthracene. These model compounds were reacted under a variety of conditions to evaluate their reactivity without coal. The reactions were performed under both thermal and catalytic conditions. Finely divided catalysts from different molybdenum precursors were used to determine their activity in promoting hydrogenation and hydrogen transfer at low severity conditions. The catalysts used were Molyvan L, sulfurized oxymolybdenum dithiocarbamate, molybdenum naphthenate, and Molyvan 822, organo molybdenum dithiocarbamate.

  14. Zinc chloride catalysis in coal and biomass liquefaction at prepyrolysis temperatures

    SciTech Connect

    Onu, C.O.; Vermeulen, T.

    1980-06-01

    Coal liquefaction processes currently under development operate with thermal decomposition of coal. This step is nonselective, and wastefully forms light hydrocarbon gases and refractory char as byproducts. It requires severe operating conditions (over 400/sup 0/C and 100 atm.), giving rise to high capital costs, and relatively low thermal efficiencies. In the present study, coal liquefaction has been investigated under milder, more selective conditions, utilizing a zinc chloride-methanol melt as a liquid-phase catalyst. Operating at 275/sup 0/C with 35 to 55 atm. of H/sub 2/, this catalytic medium has been found to give over 95% conversion of Wyodak subbituminous coal to solvent-extractible, but not yet truly liquid, products. The products are identified in a standard manner as oils, asphaltenes, and preasphaltenes, with hydrogen-to-carbon atomic ratios in the ranges of 1.2 to 1.4, 1.0 to 1.1, and 0.8 to 0.9, respectively.

  15. The dual role of oxygen functions in coal pretreatment and liquefaction: Crosslinking and cleavage reactions. First annual report, April 1, 1991--March 31, 1992

    SciTech Connect

    Serio, M.A.; Kroo, E.; Teng, H.; Charpenay, S.; Solomon, P.R.

    1992-08-01

    The overall objective of this project is elucidate and model the dual role of oxygen functions in thermal pretreatment and liquefaction of low rank coals through the application of analytical techniques and theoretical models. The project will be an integrated study of model polymers representative of coal structures, raw coals of primarily low rank, and selectivity modified coals in order to provide specific information relevant to the reactions of real coals. The investigations will include liquefaction experiments in microautoclave reactors along with extensive analysis of intermediate solid, liquid and gaseous products. Attempts will be made to incorporate the results of experiments on the different systems into a liquefaction model.

  16. Advanced direct liquefaction concepts for PETC generic units. Quarterly technical progress report, April 1993--June 1993

    SciTech Connect

    Not Available

    1993-08-01

    Section 1 contains a report of the progress by the University of Kentucky Center for Applied Energy Research on the following tasks: laboratory support (liquefaction in dewaxed and hydrotreated dewaxed solvent); CO pretreatment (effect of process variables on CO pretreatment, CO-pretreated product characterization, and liquefaction results); and iron based dispersed catalysts (production, characterization and testing of sulfated hematites and reaction model development). Section 2 contains a progress report by CONSOL, Inc. on the following tasks: laboratory support; pretreatment work on dewaxing; pretreatment work on agglomeration; and economic evaluation. Progress by Sandia National Laboratories is reported in Section 3 on the following: laboratory support (TGA methods) and solvent pretreatment (coker tar hydrogenation and coal liquefaction results). Section 4 gives a preliminary technical assessment by LDP Associates on the following: baseline economic assessment; assessment of improved coal conversion; and fluid coking.

  17. Advanced liquefaction using coal swelling and catalyst dispersion techniques. Volume 2, appendices. Final technical report, October 1, 1991--September 30, 1994

    SciTech Connect

    Curtis, C.W.; Chander, S.; Gutterman, C.

    1995-04-01

    Liquefaction experiments were undertaken using subbituminous Black Thunder mine coal to observe the effects of aqueous SO{sub 2} coal beneficiation and the introduction of various coal swelling solvents and catalyst precursors. Aqueous SO{sub 2} beneficiation of Black Thunder coal removed alkali metals and alkaline earth metals, increased the sulfur content and increased the catalytic liquefaction conversion to THF solubles compared to untreated Black Thunder coal. The liquefaction solvent had varying effects on coal conversion, depending upon the type of solvent added. The hydrogen donor solvent, dihydroanthracene, was most effective, while a coal-derived Wilsonville solvent promoted more coal conversion than did relatively inert 1-methylnaphthalene. Swelling of coal with hydrogen bonding solvents tetrahydrofuran (THF), isopropanol, and methanol, prior to reaction resulted in increased noncatalytic conversion of both untreated and SO{sub 2} treated Black Thunder coals, while dimethylsulfoxide (DMSO), which was absorbed more into the coal than any other swelling solvent, was detrimental to coal conversion. Swelling of SO{sub 2} treated coal before liquefaction resulted in the highest coal conversions; however, the untreated coal showed the most improvements in catalytic reactions when swelled in either THF, isopropanol, or methanol prior to liquefaction. The aprotic solvent DMSO was detrimental to coal conversion.

  18. Catalytic coal liquefaction. Quarterly report, October-December 1982

    SciTech Connect

    Weller, S.W.

    1983-01-01

    The catalysis of hydrogen transfer from tetralin to coal has been investigated in a tubing bomb and in an autoclave, in the absence of added hydrogen gas. On the basis of naphthalene production in tubing bomb experiments, many metals apparently increase hydrogen transfer from tetralin. Blank experiments with powdered catalyst but no coal indicate that only stannous chloride and ammonium heptamolybdate have a large effect. In the case of the molybdenum catalyst, even this effect is suspect, because blank runs with molybdate dispersed on an alumina carrier (itself non-catalytic) result in greatly increased dissociation of tetralin to naphthalene and gaseous hydrogen. Coal acts as a high-area carrier for impregnated catalyst. Thermodynamic considerations of tetralin dissociation are helpful in understanding significant differences between tubing bomb and autoclave results. When the gas:liquid volume ratio is relatively high, as in a tubing bomb, tetralin dissociation will be relatively small and equilibrium hydrogen pressure relatively high. The reverse may be true in an autoclave. Both factors lead to the expectation of higher coal conversion in a tubing bomb, in agreement with experiment.

  19. Exploratory research on solvent refined coal liquefaction. Quarterly technical progress report, January 1, 1980-March 31, 1980

    SciTech Connect

    Not Available

    1982-01-01

    This report summarizes the progress of the Exploratory Research on Solvent Refined Coal Liquefaction project by The Pittsburg and Midway Coal Mining Co.'s Merriam Laboratory for the period January 1, 1980 through March 31, 1980. A series of experiments was conducted with three western coals to study the relationship between coal properties and liquefaction behavior. All three coals were low in iron (0.2 to 0.4%, dry coal basis) and processing in both the SRC I and SRC II modes does not appear to be feasible at normal conditions without added catalyst. Adding 1 to 2% pyrite to the feed slurry increased oil yields considerably while reducing SRC and IOM yields and improved operability. Product quality was also generally improved by the catalyst. Operability and oil yields were generally found to be better at 450/sup 0/C than at 465/sup 0/C.

  20. Transition metal catalysis of hydrogen shuttling in coal liquefaction. Quarterly technical progress report, June 1, 1985-August 31, 1985

    SciTech Connect

    Eisch, J.J.

    1985-10-01

    The ultimate objective of this research is to uncover new catalytic processes for the liquefaction of coal and for upgrading coal-derived fuels by removing undesirable organosulfur, organonitrogen and organooxygen constituents. Basic to both the liquefaction of coal and the purification of coal liquids is the transfer of hydrogen from such sources as dihydrogen, metal hydrides or partially reduced aromatic hydrocarbons to the extensive aromatic rings in coal itself or to aromatic sulfides, amines and ethers. Accordingly, this study is exploring how such crucial hydrogen-transfer processes might be catalyzed by soluble, low-valent transition metal complexes under moderate conditions of temperature and pressure. By learning the mechanism whereby H2, metal hydrides or partially hydrogenated aromatics can transfer hydrogen to model aromatic compounds, under homogeneous transition-metal catalysis, we hope to identify new methods for producing superior fuels from coal.

  1. Bimetallic promotion of cooperative hydrogen transfer and heteroatom removal in coal liquefaction. Quarterly summary, June 1, 1991--August 31, 1991

    SciTech Connect

    Eisch, J.J.

    1991-10-01

    The ultimate objective of this research is to uncover new catalytic processes for the liquefaction of coal and for upgrading coal-derived fuels by removing undesirable organosulfur, organonitrogen and organooxygen constituents. Basic to both the liquefaction of coal and the purification of coal liquids is the transfer of hydrogen from such sources as dihydrogen, metal hydrides or partially reduced aromatic hydrocarbons to the extensive aromatic rings in coal itself or to aromatic sulfides, amines or ethers. Accordingly, this study is exploring how such crucial hydrogen-transfer processes might be catalyzed by soluble, low-valent transition metal complexes and/or Lewis acids under moderate conditions of temperature and pressure. By learning the mechanism whereby H{sub 2}, metal hydrides or partially hydrogenated aromatics do transfer hydrogen to model aromatic compounds, with the aid of homogeneous, bimetallic catalysts, we hope to identify new methods for producing superior fuels from coal.

  2. Coal liquefaction process streams characterization and evaluation. Characterization of coal-derived materials by field desorption mass spectrometry, two-dimensional nuclear magnetic resonance, supercritical fluid extraction, and supercritical fluid chromatography/mass spectrometry

    SciTech Connect

    Campbell, J.A.; Linehan, J.C.; Robins, W.H.

    1992-07-01

    Under contract from the DOE , and in association with CONSOL Inc., Battelle, Pacific Northwest Laboratory (PNL) evaluated four principal and several complementary techniques for the analysis of non-distillable direct coal liquefaction materials in support of process development. Field desorption mass spectrometry (FDMS) and nuclear magnetic resonance (NMR) spectroscopic methods were examined for potential usefulness as techniques to elucidate the chemical structure of residual (nondistillable) direct coal liquefaction derived materials. Supercritical fluid extraction (SFE) and supercritical fluid chromatography/mass spectrometry (SFC/MS) were evaluated for effectiveness in compound-class separation and identification of residual materials. Liquid chromatography (including microcolumn) separation techniques, gas chromatography/mass spectrometry (GC/MS), mass spectrometry/mass spectrometry (MS/MS), and GC/Fourier transform infrared (FTIR) spectroscopy methods were applied to supercritical fluid extracts. The full report authored by the PNL researchers is presented here. The following assessment briefly highlights the major findings of the project, and evaluates the potential of the methods for application to coal liquefaction materials. These results will be incorporated by CONSOL into a general overview of the application of novel analytical techniques to coal-derived materials at the conclusion of CONSOL`s contract.

  3. Catalytic two-stage coal liquefaction process having improved nitrogen removal

    DOEpatents

    Comolli, Alfred G.

    1991-01-01

    A process for catalytic multi-stage hydrogenation and liquefaction of coal to produce high yields of low-boiling hydrocarbon liquids containing low concentrations of nitogen compounds. First stage catalytic reaction conditions are 700.degree.-800.degree. F. temperature, 1500-3500 psig hydrogen partial pressure, with the space velocity maintained in a critical range of 10-40 lb coal/hr ft.sup.3 catalyst settled volume. The first stage catalyst has 0.3-1.2 cc/gm total pore volume with at least 25% of the pore volume in pores having diameters of 200-2000 Angstroms. Second stage reaction conditions are 760.degree.-870.degree. F. temperature with space velocity exceeding that in the first stage reactor, so as to achieve increased hydrogenation yield of low-boiling hydrocarbon liquid products having at least 75% removal of nitrogen compounds from the coal-derived liquid products.

  4. Process for coal liquefaction by separation of entrained gases from slurry exiting staged dissolvers

    DOEpatents

    Givens, Edwin N.; Ying, David H. S.

    1983-01-01

    There is described an improved liquefaction process by which coal is converted to a low ash and low sulfur carbonaceous material that can be used as a fuel in an environmentally acceptable manner without costly gas scrubbing equipment. In the process, coal is slurried with a solvent, passed through a preheater and at least two dissolvers in series in the presence of hydrogen-rich gases at elevated temperatures and pressures. Solids, including mineral ash and unconverted coal macerals are separated from the condensed dissolver effluent. In accordance with the improved process, fresh hydrogen is fed to each dissolver and the entrained gas from each dissolver is separated from the slurry phase and removed from the reactor system before the condensed phase is passed to the next dissolver in the series. In accordance with another process, the feeds to the dissolvers are such that the top of each downstream dissolver is used as a gas-liquid separator.

  5. Catalytic coal liquefaction. Final technical report, June 1, 1981-May 31, 1984

    SciTech Connect

    Weller, S.W.

    1984-07-01

    Molybdenum catalysts (both supported and unsupported) have been examined in various stages of preparation and use with respect to BET surface area and low temperature oxygen chemisorption. The results are detailed. X-ray diffraction has been used to characterize ammonium molybdate - after calcination, heated in tetralin under nitrogen and after use in an autoclave. Metal salts have been tested for catalytic effects by heating a tetralin-coal mixture (without hydrogen) at a loading of 1% of the coal. Only ammonium heptamolybdate and stannous chloride had a large incremental effect (based on blank runs with tetralin and catalyst without coal). Differences in liquefaction behavior in tubing bombs and in autoclaves are explained by thermodynamic considerations based on the gas to liquid volume in the two cases. (LTN)

  6. Letdown valve (anti eroded type for slurry use) on 150 t/d coal liquefaction pilot plant

    SciTech Connect

    Kamada, Mitsushi; Kobayashi, Masatoshi; Yoshida, Haruhiko; Yamagiwa, Hisashi

    1999-07-01

    The letdown valve developed by NEDO has been tested on the 150 t/d coal liquefaction pilot plant using the NEDOL process for more than 6,000 hours of on-coal operation. Several factors affecting the damage of the letdown valve that handled a fluid containing coal-derived oil, catalyst and residue including ash have been evaluated. The countermeasure for the damage has been studied to develop an advanced letdown valve to be used demonstration plant.

  7. Advanced Coal Liquefaction Research and Development Facility, Wilsonville, Alabama. Run 261 with Illinois No. 6 Burning Star Mine coal

    SciTech Connect

    Not Available

    1992-09-01

    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 Illinois No. 6 coal. Increasing viscosity and preasphaltenes made it difficult to operate at conditions similar to EXP-AO-60 catalyst operation, especially at lower catalyst replacement rates.

  8. Improved Fischer-Tropsch catalysts for indirect coal liquefaction

    SciTech Connect

    Wilson, R.B. Jr.; Tong, G.T.; Chan, Y.W.; Huang, H.W.; McCarty, J.G.

    1989-02-01

    The Fischer-Tropsch synthesis (FTS)reaction is the established technology for the production of liquid fuels from coal by an indirect route using coal-derived syngas (CO + H{sub 2}). Modern FTS catalysts are potassium- and copper-promoted iron preparations. These catalysts exhibit moderate activity with carbon monoxide-rich feedstocks such as the syngas produced by advanced coal gasification processes. However, the relatively large yields of by-product methane and high-molecular-weight hydrocarbon waxes detract from the production of desired liquid products in the C{sub 5}-C{sub 16} range needed for motor and aviation fuel. The goal of this program is to decrease undesirable portions of the FTS hydrocarbon yield by altering the Schultz-Flory polymerization product distribution through design and formulation of improved catalysts. Two approaches were taken: (1) reducing the yield of high-molecular-weight hydrocarbon waxes by using highly dispersed catalysts produced from surface-confined multiatomic clusters on acid supports and (2) suppressing methane production by uniformly pretreating active, selective conventional FTS catalysts with submonolayer levels of sulfur.

  9. Highly Dispersed Pseudo-Homogeneous and Heterogeneous Catalysts Synthesized via Inverse Micelle Solutions for the Liquefaction of Coal

    SciTech Connect

    Hampden-Smith, M.; Kawola, J.S.; Martino, A.; Sault, A.G.; Yamanaka, S.A.

    1999-01-05

    The mission of this project was to use inverse micelle solutions to synthesize nanometer sized metal particles and test the particles as catalysts in the liquefaction of coal and other related reactions. The initial focus of the project was the synthesis of iron based materials in pseudo-homogeneous form. The frost three chapters discuss the synthesis, characterization, and catalyst testing in coal liquefaction and model coal liquefaction reactions of iron based pseudo-homogeneous materials. Later, we became interested in highly dispersed catalysts for coprocessing of coal and plastic waste. Bifunctional catalysts . to hydrogenate the coal and depolymerize the plastic waste are ideal. We began studying, based on our previously devised synthesis strategies, the synthesis of heterogeneous catalysts with a bifunctional nature. In chapter 4, we discuss the fundamental principles in heterogeneous catalysis synthesis with inverse micelle solutions. In chapter 5, we extend the synthesis of chapter 4 to practical systems and use the materials in catalyst testing. Finally in chapter 6, we return to iron and coal liquefaction now studied with the heterogeneous catalysts.

  10. Liquefaction of coal by Polyporus versicolor and Poria monticola. Progress report, 1 January-31 March 1985

    SciTech Connect

    Cohen, M.S.

    1985-01-01

    Both Polyporus versicolor and Poria monticola were obtained from the American Type Culture Collection. Growth of Polyporus was shown to be faster and stronger than that of Poria under all conditions tested and the results reported here are based upon liquefaction of lignite coal by Polyporus. The liquefied coal samples were treated with acetonitrile which gave two fractions, a black precipitate and a light yellow liquid phase supernatant. This supernatant consists of acetonitrile and organic compounds which are soluble in acetonitrile. If the supernatant is drawn off with a Pasteur pipette followed by addition of water to the black precipitate, the precipitate dissolves instantly in the water producing a black liquid. Using these techniques, the products of coal liquefaction have been divided into two phases which are soluble either in acetonitrile or in water. Both fractions have been analyzed by HPLC and compounds have been partially separated. No peaks have been identified. However, two principal peaks of the acetonitrile fraction have been sent to PETC for chemical analysis by GC-MS. 9 figs.

  11. A characterization and evaluation of coal liquefaction process streams. Status assessment

    SciTech Connect

    Brandes, S.D.

    1995-07-01

    A review of the literature dealing with the modeling of fossil-fuel resid conversion to product oils and an updated assessment of the physico-chemical analytical methodology applicable to coal-liquefaction product streams is presented in this document. Analytical methodologies included here are either those which are different than those previously surveyed or are improvements on, or significantly different applications of methods previously surveyed. The literature cited spans the time period from 1991 to the present. The literature was examined from the 1960s through the present. When possible, for each model described, the methodology for deriving the model and the relative quality of the kinetic parameters derived is discussed. Proposed reaction schemes used for constructing coal-conversion models, in many cases, include the conversion of a resid intermediate to light products. These models are, therefore, also of interest, and are included here. Analytical techniques were identified that were shown to be useful for providing physico-chemical information of coal-liquefaction resids. These techniques are nuclear magnetic resonance spectroscopy, mass spectrometry (especially the technique of field ionization mass spectrometry), electron spin resonance spectroscopy coupled to thermogravimetric analysis, and a suite of petroleum inspection tests. It is recommended that these techniques be used in the present contract. 76 refs.

  12. Additive effect of waste tire on the hydrogenolysis reaction of coal liquefaction residue

    SciTech Connect

    Motoyuki Sugano; Daigorou Onda; Kiyoshi Mashimo

    2006-12-15

    A numerous amount of waste tire is landfilled or dumped all over the world, which causes environmental problems, such as destruction of natural places and the risk of fires. On the other hand, the coal liquefaction residue (CLR) is produced in 30% yield through the process supporting unit (PSU) of the NEDOL coal liquefaction process. Therefore, the investigation on an effective method for utilization of waste tire and CLR is required. In this study, the simultaneous hydrogenolysis of CLR and pulverized waste tire was carried out by using tetralin. The yields in the simultaneous hydrogenolysis were compared with algebraic sum of the yields of the individual hydrogenolyses of waste tire alone and coal alone. In the simultaneous hydrogenolysis, the synergistic effects to upgrading, such as an increase in the yield of the oil constituent and a decrease in the yield of the asphaltene constituent, occurred because of the stabilization of asphaltenic radicals from CLR with aliphatic radicals from tire. The decrease in asphaltene yield in the simultaneous hydrogenolysis was pronounced with the increase in the tire:CLR ratio because the solvent effects of liquefied tire, such as stabilization of radicals, hydrogen shuttling, and heat transfer, were enhanced. Accordingly, it is estimated that the simultaneous hydrogenolysis of CLR and waste tire is an effective method for processing both materials. 15 refs., 3 figs., 2 tabs.

  13. Characteristics of process oils from HTI coal/plastics co-liquefaction runs

    SciTech Connect

    Robbins, G.A.; Brandes, S.D.; Winschel, R.A.; Burke, F.P.

    1995-12-31

    The objective of this project is to provide timely analytical support to DOE`s liquefaction development effort. Specific objectives of the work reported here are: (1) to determine the fate of the plastics feedstocks, relative to coal-only operation; (2) to determine the conversion of the feedstocks; (3) to determine the product streams to which the feedstocks are converted (bottoms vs. distillate); (4) to determine interactions of feedstocks; (5) to determine how use of plastics feedstocks affect product quality; and (6) to determine to what degree property differences reflect feedstock differences vs. other (process) condition changes, such as unit operations, space velocity, and catalyst age.

  14. Selective enrichment of phenols from coal liquefaction oil by solid phase extraction method

    SciTech Connect

    Tian, M.; Feng, J.

    2009-07-01

    This study focuses on the solid phase extraction method for the enrichment and separation of phenol from coal liquefaction oil. The phenols' separation efficiency was compared on different solid phase extraction (SPE) cartridges, and the effect of solvents with different polarity and solubility parameter on amino-bonded silica was compared for selection of optimal elution solution. The result showed that amino-bonded silica has the highest selectivity and best extraction capability due to two factors, weak anion exchange adsorption and polar attraction adsorption.

  15. The use of mixed pyrrhotite/pyrite catalysts for co-liquefaction of coal and waste rubber tires

    SciTech Connect

    Dadyburjor, D.B.; Zondlo, J.W.; Sharma, R.K.

    1995-12-31

    The overall objective of this research program is to determine the optimum processing conditions for tire/coal co-liquefaction. The catalysts used will be a ferric-sulfide-based materials, as well as promising catalysts from other consortium laboratories. The intent here is to achieve the maximum coal+tire conversion at the mildest conditions of temperature and pressure. Specific objectives include an investigation of the effects of time, temperature, pressure, catalyst and co-solvent on the conversion and product slate of the co-liquefaction. Accomplishments and conclusions are discussed.

  16. Effects of low-temperature catalytic pretreatments on coal structure and reactivity in liquefaction. Technical progress report, August 1992--November 1992

    SciTech Connect

    Song, C.; Huang, L.; Wenzel, K.; Saini, A.K.; Burgess, C.; Hatcher, P.G.; Schobert, H.H.

    1992-12-01

    During this quarterly period progress has been made in the following three subjects related to the effects of low-temperature thermal and catalytic pretreatments on coal structure and reactivity in liquefaction. First, the liquefaction behavior of three bituminous coals with a carbon content ranging from 77% to 85% was evaluated spectroscopically by {sup 13}C NMR and pyrolysis/gas chromatography/mass spectrometry to delineate the structural changes that occur in the coal during liquefaction. Complementary data includes ultimate and proximate analysis, along with optical microscopy for maceral determinations. Even though these are all bituminous coals they exhibit quite different physical and chemical characteristics. The coals vary in rank, ranging from HvC b to HvA b, in petrographic composition, different maceral percentages, and in chemical nature, percent of carbon and of volatiles. It is these variations that govern the products, their distribution, and conversion percentages. Some of the products formed can be traced to a specific maceral group. Second, pyrolysis-GC-MS and FTIR techniques were used to characterize Wyodak coal before and after drying in vacuum and in air and the residues from its thermal and catalytic liquefactions. The analysis of the air-dried coal shows a decrease in the phenolic type structures in the coal network and increase in the carbonyl structures as the oxidative drying proceeds. An enhanced decrease in the carbonyl structure is observed in the liquefaction residues from the raw coal as compared to that of the vacuum dried coal. The analyses of the liquefaction residues of the air-dried coal show an increase in the ether linkages which may have a negative impact on liquefaction. The extent of the solvent adduction also increases during liquefaction with the extent of oxidation of the coal. Finally, the effects of reaction conditions were investigated on conversion of low-rank coals using a Texas subbituminous coal.

  17. Synthesis of model compounds for coal liquefaction research

    SciTech Connect

    Hirschon, A.S.; Asaro, M.; Bottaro, J.

    1990-11-02

    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-methyl dibenzothiophene, and (2) a 1-hydroxy naphthalene- 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 we have already submitted. Our experimental work during this quarter concentrated on Task 2: Synthesis of 4(4{prime}- hydroxy- 5{prime},6{prime},7{prime},8{prime}- tetrahydro-1{prime}- naphthylmethyl)- 6-methyldibenzothiophene. 11 refs.

  18. Low severity coal liquefaction promoted by cyclic olefins. Quarterly report, October--December 1993

    SciTech Connect

    Curtis, C.W.

    1993-12-31

    Acid pretreatment removes those alkaline metal and alkaline earth cations which inhibit coal reactivity and hydrogen transfer. Shams et al. (1992) found that through this pretreatment a large portion of the calcium present in coal was removed. Hydrochloric acid was used in that study, but sulfurous acid, if similar results are achieved, would be a much more suitable acid for processing. Another pretreatment method to remove these cations is one using ammonium acetate (Hengel and Walker, 1984). This study will evaluate the effect of combining these two principles, acid pretreatment of coal and rapid hydrogen transfer, for improving hydrogen transfer under low severity conditions. The acid pretreatment methods showed more success with low rank, subbituminous coals and lignite. Therefore, Wyodak subbituminous coal (WY) from the Argonne Premium Sample Bank and Black Thunder subbituminous coal (BT) from Amoco are being used and compared in this study. The cyclic olefin, 1,4,5,8-tetrahydronaphthalene (isotetralin, ISO) and its analogue, 1,2,3,4-tetrahydronaphthalene (tetralin, TET), will also be used and compared in this study. The efficacy of the two-ringed ISO can then be compared with the previously studied three-ringed HHA. Dr. James Hool, Professor of Industrial Engineering and an expert in statistics and experimental design, assisted in formulating the four-dimensional experimental matrix found in Figure 1. It is through this parametric analysis that the effect of each factor in this pretreatment and low severity liquefaction system will be determined.

  19. Solvent tailoring in coal liquefaction. Quarterly report, July-September 1983

    SciTech Connect

    Tarrer, A.R.; Curtis, C.W.; Guin, J.A.; Williams, D.C.

    1983-01-01

    A series of twenty-three aromatic compounds were ranked for their donor solvent efficacy for the dissolution of Western Kentucky No. 9/14 coal. The transfer of hydrogen from the solvent to the coal fragments, as measured by coal conversion, was examined at three levels of available hydrogen. The hydrogen donors are ranked according to their ability to convert coal to THF solubles. Aromatic analogs of the donors showed little ability to convert coal to THF solubles. Factors which influence hydrogen donation include the presence of heteroatoms or substituents both internal and external to the aromatic or hydroaromatic rings, the degree of hydrogenation, the aromaticity or nonaromaticity of the hydroaromatics, and the presence of five-membered rings. A relationship between heats of formation and hydrogen donor ability is shown for hydroaromatics within two ring or three ring homologous series. A model hydrogen acceptor, benzophenone, is also used to rank donors. No correlation exists in the ranking of hydrogen donors by the model acceptor used in this work and in other experimental studies and that obtained by conversion of Western Kentucky coal at typical liquefaction conditions. 24 references.

  20. Exploratory research on solvent refined coal liquefaction. Annual technical progress report, January 1-December 31, 1979

    SciTech Connect

    1980-09-01

    This report summarizes the progress of the Exploratory Research on Solvent Refined Coal Liquefaction project by The Pittsburg and Midway Coal Mining Co.'s Merriam Laboratory during 1979. In a series of experiments with varying feed gas composition, low levels (5 to 10 mole %) of carbon monoxide had little effect on the SRC II processing of Pittsburgh Seam coal (Powhatan No. 5 Mine) while higher levels (20 to 40 mole %) resulted in a general degradation of operability and reduced oil yields. Addition of finely divided (approx. 1 ..mu..m) pyrite to the reactive Powhatan coal had little effect on oil yields although the molecular weight of the distillation residue was apparently decreased. When finely divided pyrite and magnetite were added to the less reactive coals from the Loveridge and Blacksville No. 1 Mines (also Pittsburgh Seam), however, substantial increases in oil yields and product quality were obtained. In a comparison of upflow and downflow dissolver configurations with Powhatan coal in the SRC II mode, there was no difference in yields or product quality. A study characterizing specific reactors revealed a significantly higher conversion in the SRC I mode with a reactor approximating plug flow conditions compared to a completely backmixed reactor. In the SRC II mode there was only a slightly higher oil yield with the plug flow reactor.

  1. Synthesis of model compounds for coal liquefaction research. Final report, April 15, 1990--April 14, 1991

    SciTech Connect

    Not Available

    1991-11-01

    Coal liquefaction investigations required the availability of model compounds for mechanistic investigations. Towards this end, IITRI was funded to develop an approach for the synthesis of one of the target compound. This study was carried out in several phases as outlined here. Initial synthetic investigations on obtaining 2-tetrolol was carried out using high pressure and temperature reduction with Raney nickel catalyst. The next step consisted in incorporation of a hydroxymethyelene group at the C-3 position. This was successfully carried out utilizing 2-tetrolol, formaldehyde, and calcium oxide. An alternate improved method was developed using 3-carboxyl-2-naphthol. This required less time, gave a cheer product in higher yield. Efforts at the introduction of a chloromethylene group only yielded polymeric material or starting material in spite of protection the phenolic group by various groups. They synthesis of 3, 5-dimethyl-6- bromobenzyl chloride was successfully carried out by performing the Blank reaction of 2, 4-dimethyl bromobenzene. The product was characterized by GC/MS. Purification was not possible, as it was a complex mixture. Efforts at converting it to the acetate followed by separation to was not feasible. Unlike in the case of 2- hydroxyteralol, hydroxymetylation by established procedure yielded only the starting materials. Commercially available 4-methoxy-1- maphthaldehyde was protected as the ethylene acetal. The Wittig reagent 3-chlorobenzyl phosphonium bromide was prepared and condensed with 4-methoxy-1-napthaldehyde successfully and proved that the overall synthetic approach was proceeding in the desired direction. All the necessary intermediates have been synthesized,and we have demonstrated using model compounds, that the synthetic objective can be attained.

  2. Effects of low-temperature catalytic pretreatments on coal structure and reactivity in liquefaction. Technical progress report, December 1992--March 1993

    SciTech Connect

    Song, C.; Saini, A.K.; Wenzel, K.; Huang, L.; Hatcher, P.G.; Schobert, H.H.

    1993-04-01

    This work is a fundamental study of catalytic pretreatments as a potential preconversion step to low-severity liquefaction. The ultimate goal of this work is to provide the basis for the design of an improved liquefaction process and to facilitate our understanding of those processes that occur when coals are initially dissolved. The main objectives of this project are to study the effects of low-temperature pretreatments on coal structure and their impacts on the subsequent liquefaction. The effects of pretreatment temperatures, catalyst type, coal rank and influence of solvent will be examined. We have made significant progress in the following four aspects during this quarterly period: (1) influence of drying and oxidation of coal on the conversion and product distribution in catalytic liquefaction of Wyodak subbituminous coal using a dispersed catalyst; (2) spectroscopic characterization of dried and oxidized Wyodak coal and the insoluble residues from catalytic and thermal liquefaction; (3) the structural alteration of low-rank coal in low-severity liquefaction with the emphasis on the oxygen-containing functional groups; and (4) effects of solvents and catalyst dispersion methods in temperature-programmed and non-programmed liquefaction of three low-rank coals.

  3. Role of non-ferrous coal minerals and by-product metallic wastes in coal liquefaction. Technical progress report, 1 March 1980-31 May 1980

    SciTech Connect

    Garg, D; Schweighardt, F K; Givens, E N; Clinton, J H; Tarrer, A R; Guin, J A; Curtis, C W; Huang, S M

    1980-06-01

    This report describes work done in a study of the role of coal minerals and by-product metallic wastes in coal liquefaction. The thermal behavior of various minerals and metallic by-product wastes was evaluated by thermal gravimetric analysis and differential thermal analysis in the presence of hydrogen, nitrogen, and air. The CPDU was operated for 220 hours to obtain baseline data and provide information on the catalytic activity of Robena pyrite in solvent hydrogenation and coal liquefaction. A number of minerals were screened for catalytic activity toward coal liquefaction in a tubing-bomb reactor. The catalytic activity of the minerals was assessed by comparing the product distributions both in the presence of minerals and their absence. The use of a Bronson Sonifier was initiated in March to accelerate and improve the solvent separation technique. The addition of lime to the reaction mixture practically killed the liquefaction reaction. The addition of dolomite, rutile, illite, quartz, zircon, and calcite to the reaction mixture showed no significant improvement over that of a no additive run. The addition of zinc oxide and ilmenite showed slight improvement. Robena pyrite and Co-Mo-Al showed significant improvement in coal conversion and production of benzene solubles and gases. Iron oxide (Fe/sub 2/O/sub 3/) gave the highest conversion of coal and production of benzene solubles among all the minerals tested so far.

  4. Synthesis of model compounds for coal liquefaction research

    SciTech Connect

    Asaro, M.F.; Bottaro, J.C.; Hirschon, A.S.

    1991-05-01

    The objective 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 we have already submitted. Tasks 2 and 3 are as follows: Synthesis of 4(4-hydroxy-5{prime},6{prime},7{prime},8{prime}-tetrahydro-1{prime}-naphthylmethyl)-6-methyldibenzothiophene and synthesis of 1-hydroxynaphthalene-dibenzothiophene polymer linked by methylene bonds. 14 refs.

  5. Advanced direct liquefaction concepts for PETC generic units. Quarterly technical progress report, April 1994--June 1994

    SciTech Connect

    1994-09-01

    The technical approach of the contract has been expanded to provide additional economic evaluation of related process options. Additional data will be developed in the following areas to facilitate these evaluations. The effect of several modified pretreatments on liquefaction will be investigated. These include catalytic and thermal dewaxing of distillate solvents, the effect that adding light resid to distillate solvent has on hydrotreating and dewaxing, the liquefaction behavior of dense-media separated low-rank coals, and methods of selectively removing oxygen from low-rank coals. Additional chemical, physical, and performance information on improved first-stage catalysts will be developed. Upgrading of ash concentrate to recover catalysts and improve low-rank coals will be assessed. The conversion of residual fractions to distillate by hydropyrolysis will be evaluated. The economic impact of these processes will be determined.

  6. Wilsonville Advanced Coal Liquefaction Research and Development Facility, Wilsonville, Alabama. Topical report No. 14. Catalyst activity trends in two-stage coal liquefaction

    SciTech Connect

    Not Available

    1984-02-01

    The Two Stage Coal Liquefaction process became operational at Wilsonville in May 1981, with the inclusion of an H-OIL ebullated-bed catalytic reactor. The two stage process was initially operated in a nonintegrated mode and has recently been reconfigurated to fully integrate the thermal and the catalytic stages. This report focuses on catalyst activity trends observed in both modes of operation. A literature review of relevant catalyst screening studies in bench-scale and PDU units is presented. Existing kinetic and deactivation models were used to analyze process data over an extensive data base. Based on the analysis, three separate, application studies have been conducted. The first study seeks to elucidate the dependence of catalyst deactivation rate on type of coal feedstock used. A second study focuses on the significance of catalyst type and integration mode on SRC hydrotreatment. The third study presents characteristic deactivation trends observed in integrated operation with different first-stage thermal severities. In-depth analytical work was conducted at different research laboratories on aged catalyst samples from Run 242. Model hydrogenation and denitrogenation activity trends are compared with process activity trends and with changes observed in catalyst porosimetric properties. The accumulation of metals and coke deposits with increasing catalyst age, as well as their distribution across a pellet cross-section, are discussed. The effect of catalyst age and reactor temperature on the chemical composition of flashed bottoms product is addressed. Results from regenerating spent catalysts are also presented. 35 references, 31 figures, 18 tables.

  7. Thiophenic Sulfur Compounds Released During Coal Pyrolysis

    PubMed Central

    Xing, Mengwen; Kong, Jiao; Dong, Jie; Jiao, Haili; Li, Fan

    2013-01-01

    Abstract Thiophenic sulfur compounds are released during coal gasification, carbonization, and combustion. Previous studies indicate that thiophenic sulfur compounds degrade very slowly in the environment, and are more carcinogenic than polycyclic aromatic hydrocarbons and nitrogenous compounds. Therefore, it is very important to study the principle of thiophenic sulfur compounds during coal conversion, in order to control their emission and promote clean coal utilization. To realize this goal and understand the formation mechanism of thiophenic sulfur compounds, this study focused on the release behavior of thiophenic sulfur compounds during coal pyrolysis, which is an important phase for all coal thermal conversion processes. The pyrolyzer (CDS-5250) and gas chromatography–mass spectrometry (Focus GC-DSQII) were used to analyze thiophenic sulfur compounds in situ. Several coals with different coal ranks and sulfur contents were chosen as experimental samples, and thiophenic sulfur compounds of the gas produced during pyrolysis under different temperatures and heating rates were investigated. Levels of benzothiophene and dibenzothiophene were obtained during pyrolysis at temperatures ranging from 200°C to 1300°C, and heating rates ranging from 6°C/ms to 14°C/ms and 6°C/s to 14°C/s. Moreover, the relationship between the total amount of benzothiophene and dibenzothiophene released during coal pyrolysis and the organic sulfur content in coal was also discussed. This study is beneficial for understanding the formation and control of thiophenic sulfur compounds, since it provides a series of significant results that show the impact that operation conditions and organic sulfur content in coal have on the amount and species of thiophenic sulfur compounds produced during coal pyrolysis. PMID:23781126

  8. Thiophenic Sulfur Compounds Released During Coal Pyrolysis.

    PubMed

    Xing, Mengwen; Kong, Jiao; Dong, Jie; Jiao, Haili; Li, Fan

    2013-06-01

    Thiophenic sulfur compounds are released during coal gasification, carbonization, and combustion. Previous studies indicate that thiophenic sulfur compounds degrade very slowly in the environment, and are more carcinogenic than polycyclic aromatic hydrocarbons and nitrogenous compounds. Therefore, it is very important to study the principle of thiophenic sulfur compounds during coal conversion, in order to control their emission and promote clean coal utilization. To realize this goal and understand the formation mechanism of thiophenic sulfur compounds, this study focused on the release behavior of thiophenic sulfur compounds during coal pyrolysis, which is an important phase for all coal thermal conversion processes. The pyrolyzer (CDS-5250) and gas chromatography-mass spectrometry (Focus GC-DSQII) were used to analyze thiophenic sulfur compounds in situ. Several coals with different coal ranks and sulfur contents were chosen as experimental samples, and thiophenic sulfur compounds of the gas produced during pyrolysis under different temperatures and heating rates were investigated. Levels of benzothiophene and dibenzothiophene were obtained during pyrolysis at temperatures ranging from 200°C to 1300°C, and heating rates ranging from 6°C/ms to 14°C/ms and 6°C/s to 14°C/s. Moreover, the relationship between the total amount of benzothiophene and dibenzothiophene released during coal pyrolysis and the organic sulfur content in coal was also discussed. This study is beneficial for understanding the formation and control of thiophenic sulfur compounds, since it provides a series of significant results that show the impact that operation conditions and organic sulfur content in coal have on the amount and species of thiophenic sulfur compounds produced during coal pyrolysis. PMID:23781126

  9. Low severity coal liquefaction promoted by cyclic olefins. Quarterly technical progress report, April--June 1996

    SciTech Connect

    Curtis, C.W.

    1997-12-31

    The goal of this research is to develop a methodology for analyzing the reactivity of cyclic olefins in situ in a high temperature and high pressure infrared cell. Cyclic olefins, such as 1,4,5,8-tetrahydronaphthalene (isotetralin) and 1,4,5,8,9,10-hexahydroanthracene (HHA), are highly reactive donor compounds that readily donate their hydrogen to coal and model acceptors when heated to temperatures of 200{degrees}C and above. These donors are active donors in the low severity liquefaction of coal at 350{degrees}C as shown in the research performed in this project. The infrared studies are being performed in a high temperature infrared cell that was obtained from AABSPEC. Modifications to that cell have been made and have been reported in previous progress reports.

  10. EDS Coal Liquefaction Process Development. Phase V. Laboratory evaluation of the characteristics of EDS Illinois bottoms

    SciTech Connect

    Lao, T C; Levasseur, A A

    1984-02-01

    This interim report documents work carried out by Combustion Engineering, Inc. under a contract to Exxon Research and Engineering Company to develop a conceptual Hybrid Boiler design fueled by the vacuum distillation residue (vacuum bottoms) derived from Illinois No. 6 coal in the EDS Coal Liquefaction Process. This report was prepared by Combustion Engineering, Inc., and is the first of two reports on the predevelopment phase of the Hybrid Boiler program. This report covers the results of a laboratory investigation to assess the fuel and ash properties of EDS vacuum bottoms. The results of the laboratory testing reported here were used in conjunction with Combustion Engineering's design experience to predict fuel performance and to develop appropriate boiler design parameters. These boiler design parameters were used to prepare the engineering design study reported in EDS Interim Report FE-2893-113, the second of the two reports on the predevelopment phase of the Hybrid Boiler Program. 46 figures, 29 tables.

  11. Liquefaction/solubilization of low-rank Turkish coals by white-rot fungus (Phanerochaete chrysosporium)

    SciTech Connect

    Elbeyli, I.Y.; Palantoken, A.; Piskin, S.; Kuzu, H.; Peksel, A.

    2006-08-15

    Microbial coal liquefaction/solubilization of three low-rank Turkish coals (Bursa-Kestelek, Kutahya-Seyitomer and Mugla-Yatagan lignite) was attempted by using a white-rot fungus (Phanerochaete chrysosporium DSM No. 6909); chemical compositions of the products were investigated. The lignite samples were oxidized by nitric acid under moderate conditions and then oxidized samples were placed on the agar medium of Phanerochaete chrysosporium. FTIR spectra of raw lignites, oxidized lignites and liquid products were recorded, and the acetone-soluble fractions of these samples were identified by GC-MS technique. Results show that the fungus affects the nitro and carboxyl/carbonyl groups in oxidized lignite sample, the liquid products obtained by microbial effects are the mixture of water-soluble compounds, and show limited organic solubility.

  12. Microbial recovery of metals from spent coal liquefaction catalysts. Final report

    SciTech Connect

    Sperl, P.L.; Sperl, G.T.

    1995-07-01

    This project was initiated on October 1, 1989, for the purpose of recovering metals from spent coal liquefaction catalysts. Two catalyst types were the subject of the contract. The first was a Ni-No catalyst support on alumina (Shell 324), the catalyst used in a pilot scale coal liquefaction facility at Wilsonville, Alabama. The second material was an unsupported ammonium molybdate catalyst used in a pilot process by the Department of Energy at the Pittsburgh Energy Technology Center. This material was obtained in late February 1990 but has not been pursued since the Mo content of this particular sample was too low for the current studies and the studies at the Pittsburgh Energy Technology Center have been discontinued. The object of the contract was to treat these spent catalysts with microorganisms, especially Thiobacillus ferrooxidans , but also other Thiobacillus spp. and possibly Sulfolobus and other potential microorganisms, to leach and remove the metals (Ni and Mo) from the spent catalysts into a form which could be readily recovered by conventional techniques.

  13. Dispersed catalysts for co-processing and coal liquefaction

    SciTech Connect

    Bockrath, B.; Parfitt, D.; Miller, R.

    1995-12-31

    The basic goal is to improve dispersed catalysts employed in the production of clean fuels from low value hydrocarbons. The immediate objective is to determine how the properties of the catalysts may be altered to match the demands placed on them by the properties of the feedstock, the qualities of the desired end products, and the economic constraints put upon the process. Several interrelated areas of the application of dispersed catalysts to co-processing and coal conversion are under investigation. The first involves control of the selectivity of MoS{sub 2} catalysts for HDN, HDS, and hydrogenation of aromatics. A second area of research is the development and use of methods to evaluate dispersed catalysts by means of activity and selectivity tests. A micro-flow reactor has been developed for determining intrinsic reactivities using model compounds, and will be used to compare catalysts prepared in different ways. Micro-autoclaves will also be used to develop data in batch experiments at higher partial pressures of hydrogen. The third area under investigation concerns hydrogen spillover reactions between MoS{sub 2} catalysts and carbonaceous supports. Preliminary results obtained by monitoring H{sub 2}/D{sub 2} exchange reactions with a pulse-flow microreactor indicate the presence of spillover between MoS{sub 2} and a graphitic carbon. A more complete study will be made at a later stage of the project. Accomplishments and conclusions are discussed.

  14. The mechanism of hydrogen incorporation in coal liquefaction. Final report

    SciTech Connect

    1995-11-01

    The purpose of the research was to determine the detailed molecular mechanism for the introduction of hydrogen into coal when it is heated in an atmosphere of H{sub 2} in the absence of catalysts and to use this information as a baseline for the study of catalyzed processes. The plan was to study the reaction of model compounds with D{sub 2} in a glass-lined reactor of the authors` design and, by determining the distribution of D atoms in the reaction products, to deduce the reaction mechanism(s). As of the date of this report (Nov. 1995), the authors have, they believe conclusively, demonstrated the mechanism of the thermal process. They have studied several gas-phase reactions and, recently, have extended these to surface-immobilized models. The data are consistent in their support of the proposed sequence. Within the past year, they have begun to look at catalyzed hydrothermolysis and, while the work is at an early stage, they can draw a few significant conclusions, presented in the report.

  15. PROCEEDINGS: EPA/INDUSTRY FORUM ON COAL LIQUEFACTION HELD AT CHICAGO, ILLINOIS ON OCTOBER 23 AND 24, 1979

    EPA Science Inventory

    The proceedings document presentations made at the EPA/Industry Forum on Coal Liquefaction, October 23 and 24, 1979, in Chicago. The forum brought together representatives of government and industry with the goal of sharing information and increasing cooperation between the two g...

  16. Coal liquefaction processes and development requirements analysis for synthetic fuels production

    NASA Technical Reports Server (NTRS)

    1980-01-01

    Focus of the study is on: (1) developing a technical and programmatic data base on direct and indirect liquefaction processes which have potential for commercialization during the 1980's and beyond, and (2) performing analyses to assess technology readiness and development trends, development requirements, commercial plant costs, and projected synthetic fuel costs. Numerous data sources and references were used as the basis for the analysis results and information presented.

  17. Advanced liquefaction using coal swelling and catalyst dispersion techniques. Quarterly technical progress report, July--September 1992

    SciTech Connect

    Curtis, C.W.; Gutterman, C.; Chander, S.

    1992-12-31

    The experimental study of coal swelling ratios have been determined with a wide variety of solvents. Only marginal levels of coal swelling were observed for the hydrocarbon solvents, but high levels were found with solvents having heteroatom functionality. Blends were superior to pure solvents. The activity of various catalyst precursors for pyrene hydrogenation and coal conversion was measured. Higher coal conversions were observed for the S0{sub 2}-treated coal than the raw coal, regardless of catalyst type. Coal conversions were highest for Molyvan-L, molybdenum naphthenate, and nickel octoate, respectively. Bottoms processing consists of a combination of the ASCOT process coupling solvent deasphalting with delayed coking. Initial results indicate that a blend of butane and pentane used near the critical temperature of butane is the best solvent blend for producing a yield/temperature relationship of proper sensitivity and yet retaining an asphalt phase of reasonable viscosity. The literature concerning coal swelling, both alone and in combination with coal liquefaction, and the use of dispersed or unsupported catalysts in coal liquefaction has been updated.

  18. Advanced direct liquefaction concepts for PETC generic units: Phase 2. Quarterly technical progress report, July--September, 1996

    SciTech Connect

    1996-11-01

    The Advanced Direct Liquefaction Concepts Program sponsored by the DOE Pittsburgh Energy Technology Center was initiated in 1991 with the objective of promoting the development of new and emerging technology that has the potential for reducing the cost of producing liquid fuels by direct coal liquefaction. The laboratory research program (Phase I) was completed in 1995 by UK/CAER, CONSOL, Sandia National Laboratories and LDP Associates. A three year extension was subsequently awarded in October 1995 to further develop several promising concepts derived from the laboratory program. During Phase II, four continuous bench scale runs will be conducted at Hydrocarbon Technologies, Inc. using a 2 kg/hr continuous bench scale unit located at their facility in Lawrenceville, NJ. The first run in this program (ALC-1), conducted between April 19 and May 14, 1996, consisted of five test conditions to evaluate the affect of coal cleaning and recycle solvent modification. A detailed discussion of this run is included in Section Two of this report. Results obtained during this reporting period for all participants in this program are summarized.

  19. Results of u-bend stress-corrosion-cracking specimen exposures in coal-liquefaction pilot plants

    SciTech Connect

    Baylor, V.B.; Keiser, J.R.; Allen, M.D.; Howell, M.; Newsome, J.F.

    1982-04-01

    Pilot plants with capacities of up to 600 tons/d are currently demonstrating the engineering feasibility of several coal liquefaction processes including Solvent Refined Coal (SRC), Exxon Donor Solvent (EDS), and H-Coal. These plants are the first step toward commercial production of synthetic fuels. Among other factors, development of the technology depends on reliable materials performance. A concern is the application of those austenitic stainless steels necessary for general corrosion resistance, because they are susceptible to stress corrosion cracking. This cracking results from tensile stresses in combination with offensive agents such as polythionic acids, chlorides, and caustics. To screen candidate construction materials for resistance to stress corrosion cracking, we exposed racks of stressed U-bend specimens in welded and as-wrought conditions at four coal liquefaction pilot plants. Results from exposures through June 1980 were described in a previous report for exposures in the SRC plants. This report summarizes the on-site test results from June 1980 through October 1981 for the two SRC pilot plants and the H-Coal and Exxon coal liquefaction pilot plants.

  20. Advanced direct liquefaction concepts for PETC generic units, Phase 2. Quarterly technical progress report, January--March 1996

    SciTech Connect

    1996-05-01

    The aims of this research program are to advance to bench-scale testing, concepts that have the potential for making net reductions in direct coal liquefaction process costs. The research involves a teaming arrangement between the University of Kentucky Center for Applied Energy Research (CAER), Consolidation Coal Company (CONSOL), Sandia National Laboratories (SNL), and LDP Associates. Progress reports are presented for: Task 2.1.1 development of a catalyst screening test (UK/CAER); Task 2.1.2 activation of impregnated catalysts (UK/CAER); Task 2.2 laboratory support (CONSOL); Task 3 continuous operations/parametric studies (Hydrocarbon Technologies, Inc.) and; Task 4.4 conceptual design, preliminary technical assessment (LDP Associates).

  1. Fine particle clay catalysts for coal liquefaction. Quarterly technical progress report, February 9, 1993--May 8, 1993

    SciTech Connect

    Olson, E.S.

    1995-10-01

    An investigation of new methods for the production and utilization of tetralin-soluble iron oxometallate precursors for coal liquefaction catalysts was continued in this quarter. Further descriptions of the catalytic activities of the sulfided forms were obtained. The hydrogenation activities of catalysts derived from iron oxotitanate and cobalt oxoaluminate were investigated using pyrene as a the test compound, and results were compared with thermal reactions. The hydrogenation activity of iron oxotitanate was superior to other catalysts including iron oxoaluminate. The hydrogenation activity of cobalt oxoaluminate was similar to that of iron oxoaluminate reported in previous quarterly report. The liquefaction of Wyodak subbituminous coal was investigated using in situ sulfided iron oxotitanate catalyst. In order to improve the usefulness of iron oxoaluminate as a liquefaction catalyst, iron oxoaluminate was supported on acid-treated montmorillonite (K-10). Supporting the iron oxoaluminate on an acidic support significantly improved the hydrogenation activity of iron oxoaluminate. The hydrocracking activity was increased by a large factor. Thus the aluminate and titanate structures surrounding the pyrrhotite that forms during sulfidation have a beneficial effect in preventing deactivation of the iron sites, and the presence of the acidic sites in the clay results in effective catalytic synergism between catalyst and support. These clay-supported iron oxometallates are highly promising catalysts for coal liquefaction. Iron oxyhydroxide and triiron supported on acid-treated montmorillonite (K-10) were tested for the liquefaction of ion-exchanged Wyodak (IEW) to minimize effects of the coal mineral matter. Both sulfided catalysts gave very high conversions of coal to THF-soluble and heptane-soluble (oils) products.

  2. Novel nanodispersed coal liquefaction catalysts: Molecular design via microemulsion-based synthesis

    SciTech Connect

    Osseo-Asare, K.; Boakye, E.; Vaidyanathan, N.; Radovic, L.R.

    1991-10-01

    The objective of this project is to pursue the development of highly dispersed and inexpensive catalysts for improved coal solubilization and upgrading of coal liquids. A novel study of the synthesis of liquefaction catalysts of nanometer size will be carried out. It is based on the molecular design of reverse micelles (microemulsions). These surfactant-stabilized, metalbearing microdrops offer unique opportunities for synthesizing very small particles by providing a cage-like effect that limits particle nucleation, growth and agglomeration. The emphasis will be on iron- and molybdenum-based catalysts, but the techniques to be developed should also be generally applicable. The size of these very small and monodispersed particles will be accurately determined both separately and after in situ and ex situ coal impregnation. The as-prepared nanoparticles as well as the catalyst-impregnated coal or char matrix will be characterized using the following techniques: dynamic light scattering, x-ray diffraction, x-ray photoelectron spectroscopy, scanning and/or transmission electron microscopy, and selective chemisorption.

  3. Effects of low-temperature catalytic pretreatments on coal structure and reactivity in liquefaction. Technical progress report, August 1992--July 1992

    SciTech Connect

    Song, C.; Saini, A.K.; Huang, L.; Wenzel, K.; Hou, L.; Hatcher, P.G.; Schobert, H.H.

    1992-08-01

    Low-temperature catalytic pretreatment is a promising approach to the development of an improved liquefaction process- This work is a fundamental study on effects of pretreatments on coal structure and reactivity in liquefaction. The main objectives of this project are to study the coal structural changes induced by low-temperature catalytic and thermal pretreatments by using spectroscopic techniques; and to clarify the pretreatment-induced changes in reactivity or convertibility of coals in the subsequent liquefaction. This report describes the recent progress of our work. Substantial progress has been made in the spectroscopic characterization of structure and pretreatment-liquefaction reactions of a Montana subbituminous Coal (DECS-9), and thermochemical analysis of three mw and reacted bituminous coals. Temperature programmed liquefaction has been performed on three low-rank coals both in the presence and absence of dispersed molybdenum sulfide catalyst. We also performed a detailed study of the effects of mild thermal pretreatment -- drying in air and in vacuum -- on thermal and catalytic liquefaction of a Wyodak subbituminous coal. Important information on structure and structure transformation during thermal pretreatment and liquefaction reactions of low-rank coals has been derived by applying solid-state CPMAS {sup 13}C NMR and flash pyrolysis-GC-MS (Py-GC-MS) for characterization of the macromolecular network of a Montana subbituminous coal and its residues from temperature-programmed and nonprogrammed liquefaction (TPL and N-PL) at final temperatures ranging from 300 to 425{degree}C in H-donor and non-donor solvents. The results revealed that this coal contains significant quantities of oxygen-bearing structures, corresponding to about 18 O-bound C per 100 C atoms and one O-bound C per every 5 to 6 aromatic C.

  4. Comprehensive two-dimensional gas chromatography coupled to time-of-flight mass spectrometry of coal liquids produced during a coal liquefaction process

    SciTech Connect

    Jacqui F. Hamilton; Alistair. C. Lewis; Marcos Millan; Keith D. Bartle; Alan A. Herod; Rafael Kandiyoti

    2007-01-15

    Comprehensive two-dimensional gas chromatography (GC) coupled to time-of-flight mass spectrometry (MS) has been applied to the analysis of coal-derived liquids from the former British Coal Point-of-Ayr coal liquefaction plant. The feed to the hydrocracker and the resulting product were analyzed. The results refer almost exclusively to the plant-derived recycle solvent, known as the liquefaction solvent; the molecular mass range of the GC does not exceed that of the solvent. The method allows for the resolution of the numerous structural isomers of tetralin and methyl indan, one pair of hydrogen-donor (necessary for the dissolution of coal) and isomeric nondonor (that reduce the hydrogen donors) components of the recycle solvent. In addition, the n-alkanes that concentrate in the recycle solvent are easily observed in comparison with the results from one-dimensional GC-MS. 24 refs., 6 figs., 1 tab.

  5. [The mechanisms of hydrogen incorporation in coal liquefaction

    SciTech Connect

    Guthrie, R.

    1993-01-28

    In earlier reports we have describe d our efforts to understand the mechanism of deuterium incorporation during the thermolysis of 1,2-diphenylethane and 2,2,5,5-tetramethyl-3,4-diphenylhexane under D[sub 2] gas in a glass vessel. We have reported that in both of these cases, there is substantial deuterium incorporation. A summary of our conclusions follows: Conclusions previously reported for the 1,2-diphenylethane (DPE) system. 1. Benzyl radicals produced in the thermolysis react mainly with DPE to extract a hydrogen atom and produce undeuterated toluene. 2. The 1,2-diphenylethyl radicals produced are mainly responsible for the reaction with D[sub 2] to give D atoms. 3. D atoms then react with aromatic rings to form adduct radicals which are, at least in part, reconverted to D-substituted aromatics in termination steps. 4.2-Phenylethyl radicals react in a less discriminating manner, 1/3 to 1/2 of the events probably involving direct reaction with D[sub 2]. 5. A reasonable match to major product distribution can be accomplished using a model consisting of the set of ten reactions.

  6. Synthesis of model compounds for coal liquefaction research

    SciTech Connect

    Hirschon, A.S.; Asaro, M.; Bottaro, J.

    1990-11-02

    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 group. Therefore, we will investigate an alternative method, in which a hydroxy group is added in order to help direct the second metalation step to the 4' position on 4-methyldibenzothiophene.

  7. Catalytic coal liquefaction. Quarterly report, October-December 1981. [Ammonium molybdates

    SciTech Connect

    Weller, S.W.

    1981-01-01

    This research has the following scope and objectives: (1) to characterize supported molybdena catalysts, in the sulfide as well as in the oxide form, with respect to total surface area, specific surface area by oxygen chemisorption, and catalytic activity in a standardized test reaction; (2) to study the effect of preparational variables in the liquefaction of coal with efficient catalysts, with particular emphasis on molybdenum catalysts employed in very small amount. Summary of progress do date - Tubing bomb experiments on the transfer of hydrogen from tetralin to coal have been extended to a series of impregnated metal salts and two acids, all at 1% concentration. Coal conversion, moderately high even with no catalyst, is incrementally higher with all catalysts tested. Apparent hydrogen transfer, based on naphthalene produced, is also increased by all catalysts but especially by ammonium molybdate (AM) and stannous chloride (SnCl/sub 2/). Blank runs with catalyst but no coal show a finite amount of naphthalene production; except for AM and SnCl/sub 2/, the apparent catalysis of hydrogen transfer may be an artifact associated with a catalytic effect on tetralin dissociation. This question is being examined in autoclave runs, where the gas volume: liquid volume is greater. Runs at 400/sup 0/C indicate a surprising effect: both coal and AM separately catalyze tetralin dissociation, but their combined effect is greater than the sum of the individual ones (synergy). The possibility that catalytic generation of radicals from coal in turn catalyzes tetralin dissociation is being studied at 450/sup 0/C with bibenzyl as a radical generator. 3 tables.

  8. Optimization of reactor configuration in coal liquefaction. Fourth quarterly report, 1 July 1992--30 September 1992

    SciTech Connect

    Comolli, A.G.; Johanson, E.S.; Lee, L.K.; Stalzer, R.M.

    1992-12-01

    This quarterly report covers activities of optimization of Reactor Configuration in Coal Liquefaction during the period July 1--September 30, 1992, at Hydrocarbon Research, Inc. in Lawrenceville and Princeton, New Jersey. This DOE contract period is from October 1, 1991 to September 30, 1993. The overall objective of the program is to achieve a new approach to liquefaction that generates an all distillates product slate at reduced cost of about $25 per barrel of crude oil equivalent. The quarterly report covers work on Laboratory Support, Laboratory Scale Operations, Technical Assessment, and Project Management.

  9. Modeling coal liquefaction: Decomposition of 4-(1-naphthylmethyl)bibenzyl catalyzed by carbon black

    SciTech Connect

    Farcasiu, M.; Smith, C. )

    1990-01-01

    The early stages of coal liquefaction involve cleavage of methylene and ethylene bridges connecting aromatic rings. The authors modeled this process by the reaction of 4-(1-naphthylmethyl)bibenzyl (I) in the presence of a hydrogen donor (9,10-dihydrophenanthrene). The reactions were conducted over a range of temperatures (320-430{degree}C) and reaction times (30-90 min). They found that the bond between the methylene group and the naphthalene ring and the methylene to methylene bond of bibenzyl moiety are broken with equal probability. Addition of carbon black (BP 2000) as catalyst (2-10%) increases significantly the conversion of I. This particular carbon black is, a very active and selective catalyst for the cleavage of the naphthyl-to-methylene bond.

  10. Coal liquefaction process streams characterization and evaluation. Quarterly technical progress report, July 1--September 30, 1992

    SciTech Connect

    Brandes, S.D.; Winschel, R.A.; Burke, F.P.

    1992-11-01

    This is the twelfth Quarterly Technical Progress Report under DOE Contract DE-AC22-89PC89883. Major topics reported are: Summaries of the final reports produced by Lehigh University, West Virginia University, and Vander Sande Associates under the Participants Program are presented. Analytical data produced by CONSOL are provided in Appendix I for all samples employed in the Participants Program and issued with the samples to research groups in the Participants Program. A paper was presented at the 1992 US Department of Energy Pittsburgh Energy Technology Center Liquefaction Contractors` Review Conference, held in Pittsburgh September 23--24, 1992, entitled ``The Chemical Nature of Coal Liquid Resids and the Implications for Process Development``. It appears as Appendix 2 in this report.

  11. Bimetallic promotion of cooperative hydrogen transfer and heteroatom removal in coal liquefaction

    SciTech Connect

    Eisch, J.J.

    1992-04-07

    The ultimate objective of this research has been to uncover novel reagents and experimental conditions for heteroatom removal and hydrogen transfer processes, which would be applicable to the liquefaction of coal under low-severity conditions. To this end, one phase of this research has investigated the cleavage of carbon-heteroatom bonds involving sulfur, oxygen, nitrogen and halogen by subvalent transition-metal complexes. A second phase of the study has assessed the capability of the same transition-metal complexes or of organoaluminum Lewis acids to catalyze the cleavage of carbon-hydrogen bonds in aromatics and hence to promote hydrogen shuttling. Finally, a third phase of our work has uncovered a remarkable synergistic effect of combinations of transition metals with organoaluminum Lewis acids on hydrogen shuttling between aromatics and hydroaromatics. (VC)

  12. Chemistry and morphology of coal liquefaction. Annual report, October 1, 1979-September 30, 1980

    SciTech Connect

    Heinemann, H.

    1980-09-01

    The present annual report summarizes quarterly reports and includes work performed during the last quarter of fiscal 1980. The first year of this project has just been completed and much of the time and effort has been concentrated on equipment building, assembling, testing, and on staffing. This, of course, has been more true in the areas of work with spectroscopic and high pressure equipment than in organic chemical reactions. More experimental results are therefore reported in the areas of hydrogen transfer mechanisms and catalysis and organo-metallic chemistry. A few of the significant results in these and other areas are the evidence for catalysis in hydrogen transfer from tetralin; a novel and possibly very important new synthesis of alkyl aromatics from benzene, carbon monoxide, and hydrogen; the study of coals in the transmission electron microscope identifying coal macerals, minerals and metals, and leading to the possibility of observing location of and catalytic influences on pyrolysis and hydrogenation at elevated temperatures; the finding that scales formed on deactivated cobalt-molybdena-alumina-hydrogenation catalysts contain not only metals from the liquid feedstocks, but also molybdenum sulfide which must derive from migration from the catalyst interior to and beyond the surface. Insights gained in mechanisms of pyrolysis, hydrogenation, hydrogen transfer, and indirect liquefaction of coal promise to lead to improving technology by defining problem areas and showing routes to by-pass problems.

  13. Highly dispersed catalysts for coal liquefaction. Quarterly report No. 3, February 23, 1992--May 22, 1992

    SciTech Connect

    Hirschon, A.S.; Wilson, R.B. Jr.

    1992-06-08

    Iron and molybdenum complexes were studied as precursors to high dispersion catalysts for coal liquefaction. The precursors were either organometallic complexes or water soluble salts and were impregnated into coals of various ranks. The molybdenum catalysts were found to be very effective for conversion of an Illinois {number_sign}6 bituminous coal whereas the iron catalysts were not. In contrast, the iron catalysts were found to be very effective for lignite conversions. A H-donor and a non-donor conversion system were compared, using tetralin and n-hexadecane, respectively. In each case the organometallic precursor gave greater yields of toluene soluble material, with differences being most dramatic in the hexadecane system. The yields using the organometallic molybdenum precursors in hexadecane were found to be almost as great as those in the tetralin system, indicating that good catalyst precursors do not require donor solvents. The impregnation techniques were evaluated by comparing conversion yields and analyzing the products using Field Ionization Mass Spectroscopy (f.i.m.s) and FT-IR.

  14. EDS coal liquefaction process development: Phase V. Final technical progress report, Volume I

    SciTech Connect

    1984-02-01

    All objectives in the EDS Cooperative Agreement for Phases III-B through V have been achieved for the RCLU pilot plants. EDS operations have been successfully demonstrated in both the once-through and bottoms recycle modes for coals of rank ranging from bituminous to lignitic. An extensive data base detailing the effects of process variable changes on yields, conversions and product qualities for each coal has been established. Continuous bottoms recycle operations demonstrated increased overall conversion and improved product slate flexibility over once-through operations. The hydrodynamics of the liquefaction reactor in RCLU were characterized through tests using radioactive tracers in the gas and slurry phases. RCLU was shown to have longer liquid residence times than ECLP. Support work during ECLP operations contributed to resolving differences between ECLP conversions and product yields and those of the small pilot plants. Solvent hydrogenation studies during Phases IIIB-V of the EDS program focused on long term activity maintenance of the Ni-MO-10 catalyst. Process variable studies for solvents from various coals (bituminous, subbituminous, and lignitic), catalyst screening evaluations, and support of ECLP solvent hydrogenation operations. Product quality studies indicate that highly cyclic EDS naphthas represent unique and outstanding catalytic reforming feedstocks. High volumes of high octane motor gasoline blendstock are produced while liberating a considerable quantity of high purity hydrogen.

  15. Applications of polymer extrusion technology to coal processing

    NASA Technical Reports Server (NTRS)

    Lewis, D. W.

    1981-01-01

    Upon heating, many of the middle-aged bituminous coals exhibit a plasticity very similar to polyethylene for a few minutes. Plastic coal can be extruded, pelletized or molded using common plastics technology and equipment. Investigations concerning the plastic state of coals are conducted with the objective to develop techniques which will make useful commercial applications of this property possible. Experiments which show the characteristics of plastic-state coal are discussed, and problems related to a continuous extrusion of coal are considered. Probably the most significant difference between the continuous extrusion of coal and the extrusion of a thermoplastic polymer is that volatiles are continuously being released from the coal. Attention is given to aspects of dragflow, solids feeding, and melt pumping. Application potentials for plastic coal extrusion might be related to coal gasification, direct liquefaction, and coal combustion.

  16. Coal liquefaction process wherein jet fuel, diesel fuel and/or ASTM No. 2 fuel oil is recovered

    DOEpatents

    Bauman, Richard F.; Ryan, Daniel F.

    1982-01-01

    An improved process for the liquefaction of coal and similar solid carbonaceous materials wherein a hydrogen donor solvent or diluent derived from the solid carbonaceous material is used to form a slurry of the solid carbonaceous material and wherein the naphthenic components from the solvent or diluent fraction are separated and used as jet fuel components. The extraction increases the relative concentration of hydroaromatic (hydrogen donor) components and as a result reduces the gas yield during liquefaction and decreases hydrogen consumption during said liquefaction. The hydrogenation severity can be controlled to increase the yield of naphthenic components and hence the yield of jet fuel and in a preferred embodiment jet fuel yield is maximized while at the same time maintaining solvent balance.

  17. Coal liquefaction process streams characterization and evaluation. Quarterly technical progress report, January 1--March 31, 1993

    SciTech Connect

    Robbins, G.A.; Brandes, S.D.; Winschel, R.A.; Burke, F.P.

    1993-12-01

    Process oil samples from HRI Catalytic Two-Stage Liquefaction (CTSL) Bench Unit Run CC-16 (227-76) were analyzed to provide information on process performance. Run CC-16 was operated in December 1992 with Burning Star 2 Mine (Illinois 6 seam) coal to test and validate Akzo EXP-AO-60 Ni/Mo catalyst (1/16 in. extrudate). Results were compared with those of four previous HRI CTSL bench unit runs made with Ni/Mo catalysts. Major conclusions from this work are summarized. (1) Akzo EXP-AO-60 gave process oil characteristics in Run CC-16 similar to those of other Ni/Mo catalysts tested in Runs I-13, I-16, I-17, and I-18 (by our analytical and empirical test methods). No distinct performance advantage for any of the catalysts emerges from the process oil characteristics and plant performance. Thus, for commercial coal liquefaction, a number of equivalent catalysts are available from competitive commercial sources. The similarity of run performance and process oil characteristics indicates consistent performance of HRI`s bench unit operations over a period of several years; (2) Dominant effects on process oil properties in Run CC-16 were catalyst age and higher temperature operation in Periods 10--13 (Condition 2). Properties affected were the aromaticities and phenolic -OH concentrations of most streams and the asphaltene and preasphaltene concentrations of the pressure-filter liquid (PFL) 850{degrees}F{sup +} resid. The trends reflect decreasing hydrogenation and defunctionalization of the process streams with increasing catalyst age. Operation at higher temperature conditions seems to have partially offset the effects of catalyst age.

  18. Investigation on mechanism of coal liquefaction-hydrocracking of model compounds

    SciTech Connect

    Wu, J.Z.; Gao, J.S.; Hang, Y.Z.; Oelert, H.H.

    1997-12-31

    There is strong evidence for the existence of -O-CH{sub 2}- and -CH{sub 2}-CH{sub 2}-bridge linkages in coal, especially in low rank coals, so there is a close relationship between hydrocracking kinetic of model compounds and coal liquefaction. In a tube autoclave with the volume of 17 ml the hydrocracking experiments of six model compounds are carried out in the presence of tetralin. The results show that the stability order of six model compounds in hydrocracking is as follows: Ph-Ch{sub 2}-Ph > Ph-O-Ph > Ph-Ch{sub 2}-Ch{sub 2}-Ph > Ph-O-CH{sub 2}-Ph > Ph-CH{sub 2}-S-CH{sub 2}-Ph > Ph-CH{sub 2}-S-S-CH{sub 2}-Ph. Introducing 10% (in weight) of benzyl phenyl ether can increase the decomposition ratios of diphenyl methane and diphenyl ether from 4.3% to 12.6% and 18.3% to 31.5% respectively. From the hydrocracking kinetic experiments for both benzyl phenyl ether (BPE) and dibenzyl (DB), the reaction corresponds to first order. The apparent activation (DE) is 83.9 kJ/mol for BPE and 150 kJ/mol for DB in the range of temperature 330--450 C, that is, the same as coal liquefaction. The influence of initial hydrogen pressure on hydrocracking of model compounds is also described in this paper. Under the conditions of the experiments the decomposition ratios (DR) of model compounds increase linearly with the increase of initial hydrogen pressure, e.g., DR is only 34.3% under 3.0 MPa (420 C), but 56.8% can be obtained when the initial hydrogen pressure reaches 8.5 MPa. Moreover, changing the initial pressure can influence not only DR of model compounds but also their hydrocracking mechanisms. Applying Mo-Ni, Y- and 5A-sieves to hydrocracking of model compounds are all effective. For more stable compounds such as dibenzyl methane and diphenyl ether the Y-sieve is better than the Mo-Ni catalyst, but it is just contrary to crack for benzyl phenyl ether.

  19. Role of non-ferrous coal minerals and by-product metallic wastes in coal liquefaction. Technical progress report, June 1, 1980-August 31, 1980

    SciTech Connect

    Garg, D; Givens, E N; Schweighardt, F K; Clinton, J H; Tarrer, A R; Guin, J A; Curtis, C W; Huang, W J; Shridharani, K

    1980-09-01

    Additional data on the pyrite catalysis of liquefaction of Elkhorn number 3 coal are presented. The liquefaction of Elkhorn number 3 coal was significantly catalyzed by the presence of pyrite. Coal conversion, oil yield and preasphaltene conversion all increased when pyrite was added. An increase in hydrocarbon gas make accompanied by a higher hydrogen consumption were also observed. The higher activity in the presence of pyrite could be utilized by running the liquefaction step at milder conditions which would mean a lower gas make. Although we had heard reports that sulfur elimination from the SRC was improved by use of pyrite, our data showed only very small changes. Nitrogen removal from the solvent, however, was definitely observed. At 850/sup 0/F nitrogen in the oil product went from 1.61 to 1.12 on adding pyrite. This increased nitrogen removal was also seen in the added ammonia yields. Kentucky number 9 coal also responded very well to the presence of pyrite. Conversions and oil yields increased while the hydrocarbon yields decreased at both temperatures that were tested, i.e., 825 and 850/sup 0/F. Hydrogen consumptions also increased. In the screening program the results from testing a number of materials are reported. None of the zeolites gave any significant improvement over coal itself. The iron, molybdenum, nickel, and cobalt rich materials had significant activity, all 85 to 90% conversion with high oil yields.Among materials specifically reported this period the clays failed to show any significant catalytic effect.

  20. Microwave-assisted direct liquefaction of Ulva prolifera for bio-oil production by acid catalysis.

    PubMed

    Zhuang, Yingbin; Guo, Jingxue; Chen, Limei; Li, Demao; Liu, Junhai; Ye, Naihao

    2012-07-01

    Production of bio-oil by microwave-assisted direct liquefaction (MADL) of Ulva prolifera was investigated, and the bio-oil was analyzed by elementary analysis, Fourier transform infrared spectroscopic analysis (FT-IR), and gas chromatography-mass spectrometry (GC-MS). The results indicate that the liquefaction yield is influenced by the microwave power, liquefaction temperature, liquefaction time, catalyst content, solvent-to-feedstock ratio and moisture content. The maximum liquefaction yield of U. prolifera (moisture content of 8%) was 84.81%, which was obtained under microwave power of 600 W for 30 min at 180 °C with solvent-to-feedstock ratio of 16:1 and 6% H(2)SO(4). The bio-oil was composed of benzenecarboxylic acid, diethyl phthalate, long-chain fatty acids (C(13) to C(18)), fatty acid methyl esters and water. The results suggest that U. prolifera is a viable eco-friendly, green feedstock substitute for biofuels and chemicals production. PMID:22609667