WO2009059369A1 - Liquefaction process - Google Patents
Liquefaction process Download PDFInfo
- Publication number
- WO2009059369A1 WO2009059369A1 PCT/AU2008/001649 AU2008001649W WO2009059369A1 WO 2009059369 A1 WO2009059369 A1 WO 2009059369A1 AU 2008001649 W AU2008001649 W AU 2008001649W WO 2009059369 A1 WO2009059369 A1 WO 2009059369A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- carbonaceous material
- solid carbonaceous
- process according
- carbon dioxide
- supercritical carbon
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
- C10G1/04—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by extraction
- C10G1/042—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by extraction by the use of hydrogen-donor solvents
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
- C10G1/08—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal with moving catalysts
- C10G1/083—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal with moving catalysts in the presence of a solvent
Definitions
- the present invention relates to a liquefaction process, in particular to a liquefaction process for solid carbonaceous materials, such as for example sub-bituminous coal and lignite.
- Indirect liquefaction involves gasification of the carbonaceous material followed by chemical processing at high pressure to yield a variety of liquid hydrocarbons.
- Direct liquefaction involves hydrogenation of the carbonaceous material under elevated temperatures and pressures to form a liquid plus a solid residue.
- direct liquefaction demonstrates higher thermal efficiency and potentially lower processing costs than indirect liquefaction.
- Direct liquefaction requires addition of hydrogen to the carbonaceous material so that the H/C ratio is increased to a range where the resulting product is a hydrocarbonaceous liquid.
- This process is frequently referred to as hydroconversion.
- the liquids produced typically may contain about 70% hydrocarbons (hydro- and polyhydroaromatics) , 8% heterocyclic compounds (mostly ethers) , 10% monophenols (predominantly less than 10 carbon atoms) and 12% polyphenols and basic nitrogen compounds.
- the total liquid may be composed of the following compounds: naphthalene, methylnaphthalene, biphenyl, diphenyl ether, phenathrene and/or anthracene, and pyrene .
- a substantial portion of the basic nitrogen compounds present may be quinolines. It is expected such hydrocarbonaceous liquids may be suitable for further processing in a similar manner to crude petroleum products, or as a heavy fuel oil for use in boilers and such like. Hydroconversion reactions rely on low temperature pyrolysis processes which occur in a temperature range between 350°C and 550 0 C.
- Pyrolysis reactions include loss of hydroxyl groups, dehydrogenation of some aromatics, cleavage of methylene bridges, and rupture of alicyclic rings, all leading to generation of free radical species which participate in rapid secondary reactions .
- the products of these reactions are very dependent upon the availability of hydrogen by means of free hydrogen or a hydrogen donor solvent, and the presence of catalysts.
- the present invention seeks to overcome at least some of the above mentioned disadvantages.
- the invention provides a process for producing a hydrocarbonaceous liquid from a solid carbonaceous material .
- the present invention provides a process for producing a hydrocarbonaceous liquid from a solid carbonaceous material comprising the steps of : a) providing a slurry of the solid carbonaceous material, a catalyst, and a hydrogen donor solvent and reacting the slurry with supercritical carbon dioxide whereby at least a portion of the solid carbonaceous material is converted to the hydrocarbonaceous liquid; and, b) recovering the hydrocarbonaceous liquid.
- the present invention seeks to provide a simple relatively low cost process for efficient liquefaction of carbonaceous materials, in particular brown coal and lignite, into a hydrocarbonaceous liquid that can be used as a feedstock for the production of fuel or fuel supplements .
- the reaction is performed at a temperature in a range of about 350°C to about 500° C and a pressure in a range of about 500 psi to 3000 psi.
- the reaction can be performed where the temperature is in a range of about 350° C to about 380° C and the pressure is in a range of about 500 psi to 1500 psi.
- the solid carbonaceous material is pre-treated by providing a mixture of the solid carbonaceous material, the catalyst, and a diluent and reacting the mixture with supercritical carbon dioxide.
- the hydrogen donor solvent is then added to the pre-treated mixture to provide said slurry and the hydroconversion reaction of step a) is performed.
- the pre-treatment of the solid carbonaceous material as defined above improves dispersion of the catalyst in the solid carbonaceous material and swells the particles of the solid carbonaceous material.
- the increased surface area of the pre-treated particles and dispersion of the catalyst improves the availability of solid carbonaceous material in the subsequent hydroconversion reaction thereby resulting in shorter reaction times and increased yields.
- a process for improving the dispersion of a catalyst in a solid carbonaceous material comprising providing a mixture of the solid carbonaceous material, the catalyst, and a diluent and reacting the mixture with supercritical carbon dioxide .
- a process for swelling particles of solid carbonaceous material comprising treating the particle of solid carbonaceous material with supercritical carbon dioxide.
- Figure 1 is a direct injection gas chromatography mass spectrograph (GCMS) of a THF soluble liquid obtained from the reaction products of the process for producing hydrocarbonaceous liquids from a solid carbonaceous material in accordance with the present invention and as described with reference to the Example;
- GCMS gas chromatography mass spectrograph
- Figure 2 is an enlargement of the area of Figure 1 marked Enlargement 1;
- Figure 3 is an enlargement of the area of Figure 1 marked Enlargement 2;
- Figure 4 is an enlargement of the area of Figure 1 marked Enlargement 3.
- the present invention relates to a process for producing a hydrocarbonaceous liquid from a solid carbonaceous material wherein the solid carbonaceous material is subjected to a hydroconversion reaction with a hydrogen donor solvent and super critical carbon dioxide in the presence of a catalyst to produce hydrocarbonaceous liquid.
- the hydroconversion reaction is performed at elevated temperature and pressure .
- the solid carbonaceous material prior to performing the hydroconversion reaction is pre- treated with super critical carbon dioxide to swell the particles of solid carbonaceous material. Even more preferably, prior to performing the hydroconversion reaction the solid carbonaceous material is mixed with a catalyst and a diluent, and the mixture is treated with super critical carbon dioxide to swell the particles of solid carbonaceous material while at the same time improving the dispersion of the catalyst within the swelled particles.
- the process of the present invention can be used to convert any solid carbonaceous material to hydrocarbonaceous liquids.
- solid carbonaceous material include, but are not limited to, coal, biomass, solid organic waste material such as tyre refuse, shale oil, tar sand bitumen and the like, and mixtures thereof.
- the invention is particularly useful in the hydroconversion of coal and may be used to liquefy any of the coals known in the prior art including bituminous coal, sub-bituminous coal, lignite, peat, brown coal and the like.
- the particle size or particle size range of the solid carbonaceous material is not believed to be critical to the invention, although small particle sizes are preferred wherein the surface area to particle diameter ratio favours increased hydroconversion reaction rates.
- the solid carbonaceous material is ground to a particle size of 200- 300 mesh. After sizing the solid carbonaceous material particles, a slurry of the solid carbonaceous material, a hydrogen donor solvent, and a catalyst is prepared. Typically, the ratio of hydrogen donor solvent to solid carbonaceous material will be within a range of about 1:1 to about 5:1 on a weight basis.
- the weight basis is not necessarily calculated on a moisture- free basis with respect to the solid carbonaceous material as will be explained later, and a larger excess of hydrogen donor solvent may only be required under some circumstances to ensure that the slurry is sufficiently fluid to be readily transported through pipework and the like .
- the hydrogen donor solvent is one suitable for the hydroconversion of solid carbonaceous materials to hydrocarbonaceous liquids.
- the hydrogen donor solvent may include mixtures of one or more hydrogen donor compounds .
- Illustrative examples of hydrogen donor solvents include, but are not limited to, indanes, the dihydronaphthalenes, the Ci 0 -Ci 2 tetrahydronaphthalenes, the hexahydrofluorenes, the dihydro-tetrahydro-hexahydro- and octahydropheanthrenes, the Ci 2 -Ci 3 acenaphthenes , the tetrahydro-hexahydro-and decahydropyrenes , the di-tetra- and octohydroanthracenes and other derivatives of partially saturated aromatic compounds.
- the hydrogen donor solvents may also be selected from distillate fractions of hydrocarbonaceous liquids derived from hydroconversion of carbonaceous materials, in particular coal oils derived from coal liquefaction processes. It will be appreciated that the solid carbonaceous material may be soluble, at least in part, in the hydrogen donor solvent, in particular under the process conditions of the hydroconversion reaction.
- the catalyst is one suitable for the hydroconversion of solid carbonaceous materials to hydrocarbonaceous liquids, in particular a hydrogenation catalyst.
- the catalyst may include mixtures of one or more catalysts or mixtures of one or more catalyst precursors which may be converted to an active hydrogenation catalyst under the hydroconversion reaction conditions of the present invention.
- suitable catalysts include those comprising one or more Group VIII metals, one or more Group VI metals, and combinations of one or more metals from Group VIII and Group VI, in particular iron, molybdenum, cobalt, nickel, chromium, tungsten and the noble metals including platinum, palladium, iridium, osmium ruthenium and rhodium.
- Such catalysts may be supported on an inert matrix formed from alumina, silica alumina or a similar support.
- suitable catalysts include inorganic metal compounds such as metal halides, oxyhalides, oxides, sulfides, heteropoly acids (eg. phosphomolybdic acid and molybdosilic acid) and the like; metal complexes such as metal chelates, metal complexes of organic amines, metal complexes of organic carboxylic acids, and the like,- and organometallic compounds, all of the foregoing having one or more metals selected from the group consisting of Group VIII and Group VI metals as described above.
- the ratio of catalyst to solid carbonaceous material in the slurry will be within a range of about 1 to 20% w/w.
- the catalyst may be dissolved or dispersed in a suitable diluent prior to preparing the slurry, and may be converted in situ to the active catalyst species as the slurry is heated to hydroconversion temperatures.
- the diluent will be selected on the basis of the solubility of the catalyst therein.
- Illustrative examples of the diluent include, but are not limited to, water, methanol, ethanol, acetonitrile, and aprotic solvents such as dimethylsulfoxide and dimethylformamide, and mixtures of one or more thereof.
- the slurry is prepared by dispersing the sized solid carbonaceous material in the hydrogen donor solvent together with the catalyst.
- the sized solid carbonaceous material undergoes a pre-treatment to swell the particles of the solid carbonaceous material and improve the dispersion of the catalyst in the particles.
- the slurry is prepared by dispersing the pre-treated solid carbonaceous material in the hydrogen donor solvent in the desired ratio, and there is no necessity to mix the catalyst into the slurry as it has already been dispersed in the solid carbonaceous material during the pre-treatment reaction.
- the hydroconversion of the solid carbonaceous material to hydrocarbonaceous liquid is accomplished by reacting the slurry in the presence of supercritical carbon dioxide under conditions where the temperature is in a range of about 350° C to about 500° C and the pressure is in a range of about 500 psi to 3000 psi.
- the reaction is performed where the temperature is in a range of about 350° C to about 380° C and the pressure is in a range of about 500 psi to 1500 psi.
- the hydroconversion reaction will be performed in a pressure vessel adapted to maintain conditions under which supercritical carbon dioxide can be delivered to the reaction mixture and maintained.
- Supercritical carbon dioxide refers to carbon dioxide that is in a fluid state while also being at or above both its critical temperature (31.1 °C) and pressure (73 atm) .
- Hydroconversion of the solid carbonaceous material to a hydrocarbonaceous liquid is performed at the above described conditions for a period in a range of about 15 minutes to 480 minutes. In general, the hydroconversion of the solid carbonaceous material may be accomplished in a batch or a continuous operation.
- the inventors opine that the relatively mild temperature conditions and fast reaction rates observed in the hydroconversion reaction of the present invention are obtainable by virtue of the use of supercritical carbon dioxide which facilitates increased penetration of the hydrogen donor solvent in the pores of the particles of the carbonaceous material .
- the hydroconversion of solid carbonaceous material in accordance with the present invention produces three phases: a gaseous product, the hydrocarbonaceous liquid, and a solid residue product, each of which may be separated into the respective phases by methods well known and understood to the person skilled in the art.
- the hydrocarbonaceous liquid may be recovered by distillation, centrifugation, filtration, and the like.
- Both the hydrocarbonaceous liquid and the solid residue product may be contaminated with catalyst or spent catalyst, and known techniques may be used to separate the catalyst or spent catalyst from the reaction products.
- the inventors have found that the pre-treatment of sized solid carbonaceous material with supercritical carbon dioxide in the presence of the catalyst results in several advantages which assist the performance of the subsequent hydroconversion reaction described above.
- the supercritical carbon dioxide is very efficient at penetrating the porous structure of the sized particles of solid carbonaceous material and swelling the sized particles, thereby increasing the surface area of the particles and its availability to the subsequent hydroconversion reaction.
- the pre-treatment with supercritical carbon dioxide improves the dispersion of the catalyst into the sized particles which, in turn, improves the efficiency of the hydroconversion reaction.
- sulphur, nitrogen, sodium, calcium, etc are transferred from the sized particles of carbonaceous material into the diluent.
- the diluent is water
- This feature of the present invention is advantageous in comparison with prior art processes for the liquefaction of carbonaceous material where it is typically essential to remove all surface moisture and at least some inherent moisture from the carbonaceous material prior to commencing hydroconversion reactions.
- the drying process required in prior art processes adds significantly to the overall capital and operating costs and releases significant amounts of carbon dioxide to the atmosphere.
- the solid carbonaceous material may be pre- treated by first forming a mixture of the solid carbonaceous material, a catalyst and the diluent in which the catalyst is at least partially soluble.
- the ratio of catalyst to solid carbonaceous material will be within a range of about 1 to 20% w/w, as described above .
- the mixture is placed in a pressure vessel adapted to maintain conditions under which supercritical carbon dioxide can be delivered to the reaction mixture and maintained.
- Pre-treatment of the solid carbonaceous material in the presence of supercritical carbon dioxide is performed under conditions where the temperature is in a range of about 50 0 C to about 250 0 C and the pressure is in a range of about 500 psi to 3000 psi for a period in a range of about 60 minutes to 480 minutes.
- the pre-treatment of the solid carbonaceous material may be accomplished in a batch or a continuous operation.
- a desired volume of hydrogen donor solvent as described above may be directly added to the pre-treated mixture in the pressure vessel, and the contents thereof may then be placed under conditions where the hydroconversion reaction in accordance with the present invention proceeds as described above.
- Brown coal (Loy Yang, Table 1) was ground to fine (approximately 300 mesh) particles.
- Pre-swelling and Catalyst Dispersal Coal 50 g was mixed with 10 g ferric chloride (Sigma) and 50 mL of water and the resulting slurry was stirred at room temperature for 2 hours. The slurry was then placed in a 600 mL PARR (5500 series) stirred reactor. The reactor was sealed and pressurized to 800 psi with carbon dioxide gas . The reactor contents were then heated to 80 0 C (as measured by an internal temperature sensor) for 3 hours. The reactor pressure reached approximately 1000 psi during the reaction.
- the pre-swollen coal was then mixed with 200 mL tetralin (1, 2, 3 ,4-tetrahydronaphtalene) and placed in a 600 mL PARR (5500 series) stirred reactor.
- the reactor was sealed and pressurized to 100 psi with carbon dioxide gas. Following leak testing, the reactor was then heated up to 375 0 C. The reaction was allowed to proceed for 30 minutes at 375 0 C with stirring. The maximum reaction pressure increased to 2650 psi.
- the reactor was then cooled to room temperature and opened following pressure release. The coal liquefaction products were then analysed.
- the contents of the reactor were poured into a large beaker and washed several times with THF to remove any residual coal products.
- the THF washes were added to the beaker.
- the coal liquefaction products were then filtered through a Buchner funnel with a Whatman's No. 5 filter paper (2.6 ⁇ m pore) using a water pump.
- the filter paper was washed with excess THF to ensure all coal liquids were collected.
- the filter paper was then dried in an oven at 110 0 C until its weight remained constant (ca. 30 min.) and then weighed.
- the filter was then washed with concentrated hydrochloric acid, then rinsed with water and dried at 110 0 C until a constant weight (ca. 1 hour) .
- the filter was then reweighed.
- the residual solid (12.0 g) on the filter paper is the THF insoluble coal fraction.
- coal liquids filtrate was placed in a round bottomed flask attached to a rotary evaporator and the solvent was removed by evaporation under reduced pressure.
- the combined weight of pre-asphaltenes and asphaltenes in the coal sample is 2 g.
- toluene insolubles pre-asphaltenes
- the toluene insolubles were determined using the same procedure as used for the hexane insolubles, except that toluene was used instead of hexane.
- the weight of pre-asphaltenes in the coal sample is 0.22 g, and the weight of asphaltenes in the coal sample is 1.78 g.
- the pre- treatment of coal with supercritical carbon dioxide and water at 80 0 C and 1000 psi facilitates swelling of the coal particles to about 1.5 times in volume.
- the appearance of the coal remains as very fine discrete particles.
- GCMS direct injection gas chromatography mass spectrometry
- Parameters which are determined by difference from, or summing of, measured coal parameters can be determined on individual coal sample analyses or weighted average analyses, but cannot logically be determined for the percentile distribution data. Parameters particularly effected by this constraint are marked na (not applicable), and include the fixed carbon and oxygen figures, the calculated ash, total (sum of) minerals and inorganics and the ash composition data.
- the Oxygen by difference figure is based on the balance after summing the individual organic elements and the minerals and inorganic components.
- the following table illustrates the realtively small effect of using the ash content instead of the total minerals and inorganics (see Note 1 in relation to there being no 'ash' in the coal) to determine the oxygen by difference.
- the main table uses the Minerals and Inorganics figure as more accurately estimating the organic oxygen in the coal
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
Description
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Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
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AU2008324768A AU2008324768A1 (en) | 2007-11-06 | 2008-11-06 | Liquefaction process |
Applications Claiming Priority (2)
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AU2007906115 | 2007-11-06 | ||
AU2007906115A AU2007906115A0 (en) | 2007-11-06 | Liquefaction process |
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WO2009059369A1 true WO2009059369A1 (en) | 2009-05-14 |
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PCT/AU2008/001649 WO2009059369A1 (en) | 2007-11-06 | 2008-11-06 | Liquefaction process |
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AU (1) | AU2008324768A1 (en) |
WO (1) | WO2009059369A1 (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103555353A (en) * | 2013-08-26 | 2014-02-05 | 福建农林大学 | Method for catalyzing liquefaction of plant raw material by supercutical fluid |
US20140101986A1 (en) * | 2012-10-12 | 2014-04-17 | Massachusetts Institute Of Technology | Method for Preparing a Slurry of Pulverized Solid Material in Liquid or Supercritical Carbon Dioxide |
US10077334B2 (en) | 2015-08-06 | 2018-09-18 | Instituto Mexicano Del Petróleo | Use of polymers as heterogeneous hydrogen donors in the upgrading of heavy and extra-heavy crudes |
CN110835569A (en) * | 2019-11-21 | 2020-02-25 | 山西焦煤集团有限责任公司 | Method for removing organic sulfur in coal by using supercritical fluid hydrogenation reaction |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110835570A (en) * | 2019-11-21 | 2020-02-25 | 山西焦煤集团有限责任公司 | Test method for removing organic sulfur from coal by using swelling reaction to assist mass transfer effect of supercritical fluid extraction |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4250014A (en) * | 1978-08-21 | 1981-02-10 | Exxon Research & Engineering Co. | Coal liquefaction process |
GB2063906A (en) * | 1979-11-20 | 1981-06-10 | Inst Chemii Przemyslowej | Coal liquefaction |
US4485003A (en) * | 1981-08-25 | 1984-11-27 | Fried. Krupp Gesellschaft Mit Beschrankter Haftung | Supercritical extraction and simultaneous catalytic hydrogenation of coal |
US4839030A (en) * | 1988-05-27 | 1989-06-13 | Hri, Inc. | Coal liquefaction process utilizing coal/CO2 slurry feedstream |
-
2008
- 2008-11-06 WO PCT/AU2008/001649 patent/WO2009059369A1/en active Application Filing
- 2008-11-06 AU AU2008324768A patent/AU2008324768A1/en not_active Abandoned
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4250014A (en) * | 1978-08-21 | 1981-02-10 | Exxon Research & Engineering Co. | Coal liquefaction process |
GB2063906A (en) * | 1979-11-20 | 1981-06-10 | Inst Chemii Przemyslowej | Coal liquefaction |
US4485003A (en) * | 1981-08-25 | 1984-11-27 | Fried. Krupp Gesellschaft Mit Beschrankter Haftung | Supercritical extraction and simultaneous catalytic hydrogenation of coal |
US4839030A (en) * | 1988-05-27 | 1989-06-13 | Hri, Inc. | Coal liquefaction process utilizing coal/CO2 slurry feedstream |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20140101986A1 (en) * | 2012-10-12 | 2014-04-17 | Massachusetts Institute Of Technology | Method for Preparing a Slurry of Pulverized Solid Material in Liquid or Supercritical Carbon Dioxide |
WO2014058977A1 (en) * | 2012-10-12 | 2014-04-17 | Massachusetts Institute Of Technology | Method for preparing a slurry of pulverized solid material in liquid or supercritical carbon dioxide |
CN103555353A (en) * | 2013-08-26 | 2014-02-05 | 福建农林大学 | Method for catalyzing liquefaction of plant raw material by supercutical fluid |
CN103555353B (en) * | 2013-08-26 | 2016-10-05 | 福建农林大学 | A kind of method of supercritical fluid catalytic liquefaction plant material |
US10077334B2 (en) | 2015-08-06 | 2018-09-18 | Instituto Mexicano Del Petróleo | Use of polymers as heterogeneous hydrogen donors in the upgrading of heavy and extra-heavy crudes |
CN110835569A (en) * | 2019-11-21 | 2020-02-25 | 山西焦煤集团有限责任公司 | Method for removing organic sulfur in coal by using supercritical fluid hydrogenation reaction |
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AU2008324768A1 (en) | 2009-05-14 |
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