AU2008324768A1

AU2008324768A1 - Liquefaction process

Info

Publication number: AU2008324768A1
Application number: AU2008324768A
Authority: AU
Inventors: Denis Samuel Ballantyne; John Rodney Warmington
Original assignee: ADVANCED BIOFUELS Ltd
Current assignee: ADVANCED BIOFUELS Ltd
Priority date: 2007-11-06
Filing date: 2008-11-06
Publication date: 2009-05-14
Also published as: WO2009059369A1

Description

WO 2009/059369 PCT/AU2008/001649 1 LIQUEFACTION PROCESS Field of the Invention 5 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. 10 Background of the Invention There are several processes which may be employed to produce hydrocarbonaceous liquids from solid carbonaceous materials, such as for example coal, that are generally 15 classified as either indirect or direct liquefaction. 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 20 carbonaceous material under elevated temperatures and pressures to form a liquid plus a solid residue. In general, direct liquefaction demonstrates higher thermal efficiency and potentially lower processing costs than indirect liquefaction. 25 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 30 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 35 compounds. Of these classes of compounds, about 30-50% of WO 2009/059369 PCT/AU2008/001649 2 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 5 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. 10 Hydroconversion reactions rely on low temperature pyrolysis processes which occur in a temperature range between 350 0 C and 550 0 C. Pyrolysis reactions include loss of hydroxyl groups, dehydrogenation of some aromatics, cleavage of methylene bridges, and rupture of alicyclic 15 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. 20 The present invention seeks to overcome at least some of the above mentioned disadvantages. Summary 25 In its broadest aspect, the invention provides a process for producing a hydrocarbonaceous liquid from a solid carbonaceous material. 30 In a first aspect, 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 35 and reacting the slurry with supercritical carbon WO 2009/059369 PCT/AU2008/001649 3 dioxide whereby at least a portion of the solid carbonaceous material is converted to the hydrocarbonaceous liquid; and, b) recovering the hydrocarbonaceous liquid. 5 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 10 as a feedstock for the production of fuel or fuel supplements. In one embodiment of the invention the reaction is performed at a temperature in a range of about 350*C to 15 about 500 0 C and a pressure in a range of about 500 psi to 3000 psi. In particular, 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. 20 In another embodiment of the invention prior to step (a), 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 25 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. 30. Advantageously, 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. In this way, the increased surface area of the pre-treated 35 particles and dispersion of the catalyst improves the availability of solid carbonaceous material in the WO 2009/059369 PCT/AU2008/001649 4 subsequent hydroconversion reaction thereby resulting in shorter reaction times and increased yields. Accordingly, in a second aspect there is provided a 5 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. 10 In a third aspect, there is provided a process for swelling particles of solid carbonaceous material comprising treating the particle of solid carbonaceous material with supercritical carbon dioxide. 15 Description of the Figures Accompanying the Description Figure 1 is a direct injection gas chromatography mass spectrograph (GCMS) of a THF soluble liquid obtained 20 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; Figure 2 is an enlargement of the area of Figure 1 25 marked Enlargement 1; Figure 3 is an enlargement of the area of Figure 1 marked Enlargement 2; and Figure 4 is -an enlargement of the area of Figure 1 marked Enlargement 3. 30 Detailed Description of Preferred Embodiment The present invention relates to a process for producing a hydrocarbonaceous liquid from a solid carbonaceous 35 material wherein the solid carbonaceous material is subjected to a hydroconversion reaction with a hydrogen donor solvent and super critical carbon dioxide in the WO 2009/059369 PCT/AU2008/001649 5 presence of a catalyst to produce hydrocarbonaceous liquid. The hydroconversion reaction is performed at elevated temperature and pressure. 5 Preferably, prior to performing the hydroconversion reaction the solid carbonaceous material 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 10 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. 15 In general, the process of the present invention can be used to convert any solid carbonaceous material to hydrocarbonaceous liquids. Suitable examples of solid carbonaceous material include, but are not limited to, 20 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 25 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 30 the invention, although small particle sizes are preferred wherein the surface area to particle diameter ratio favours increased hydroconversion reaction rates. In a preferred embodiment of the invention the solid carbonaceous material is ground to a particle size of 200 35 300 mesh.

WO 2009/059369 PCT/AU2008/001649 6 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 5 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 10 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 15 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, 20 the C 10

-C

1 2 tetrahydronaphthalenes, the hexahydrofluorenes, the dihydro-tetrahydro-hexahydro- and octahydropheanthrenes, the . C 12 -C1 3 acenaphthenes, the tetrahydro-hexahydro-and decahydropyrenes, the di-tetra and octohydroanthracenes and other derivatives of 25 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 30 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. 35 The catalyst is one suitable for the hydroconversion of solid carbonaceous materials to hydrocarbonaceous liquids, in particular a hydrogenation catalyst. The catalyst may WO 2009/059369 PCT/AU2008/001649 7 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. 5 Illustrative examples of 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 10 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. Other illustrative examples of suitable catalysts include inorganic metal compounds 15 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 20 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. In general, the ratio of catalyst to solid carbonaceous 25 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. In .30 general, 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 35 of one or more thereof.

WO 2009/059369 PCT/AU2008/001649 8 The slurry is prepared by dispersing the sized solid carbonaceous material in the hydrogen donor solvent together with the catalyst. As mentioned previously, in the preferred embodiment of the invention, prior to 5 performing the hydroconversion reaction, 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. Where pre-treatment has already occurred the slurry is 10 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. 15 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 20 about 350 0 C to about 500 0 C and the pressure is in a range of about 500 psi to 3000 psi. Preferably, the reaction is performed where the temperature is in a range of about 350 0 C to about 380 0 C and the pressure is in a range of about 500 psi to 1500 psi. 25 Typically, 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 30 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 35 period in a range of about 15 minutes to 480 minutes. In general, the hydroconversion of the solid carbonaceous WO 2009/059369 PCT/AU2008/001649 9 material may be accomplished in a batch or a continuous operation. While not wishing to be bound by theory, the inventors 5 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 10 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 15 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. In general, the hydrocarbonaceous liquid may be recovered by 20 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. 25 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 30 hydroconversion reaction described above. 'Firstly, the supercritical carbon dioxide is very. efficient at penetrating the porous structure of the sized particles of solid carbonaceous material and swelling the 35 sized particles, thereby increasing the surface area of the particles and its availability to the subsequent hydroconversion reaction.

WO 2009/059369 PCT/AU2008/001649 10 Secondly, 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. 5 Further, the inventors have observed that the presence of water in the pre-treatment reaction demonstrates no deleterious effects and may even assist in catalyst dispersal. Under supercritical conditions carbon dioxide 10 shows similar solvent properties to hexane, a solvent in which the catalysts of the present invention show little or no solubility. It is therefore important to dissolve or disperse the catalyst in a diluent, such as water, in the mixture of solid carbonaceous material and the 15 catalyst prior to pre-treatment to ensure effective dispersal of the catalyst in the solid carbonaceous material. The advantages arising from tolerating a polar solvent as the diluent includes the fact that during pre treatment, inorganic impurities (eg. sulphur, nitrogen, 20 sodium, calcium, etc) are transferred from the sized particles of carbonaceous material into the diluent. Additionally, and in particular when the diluent is water, there is no necessity to subject the solid carbonaceous material to a drying . process to remove water. This 25 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 30 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. 35 Accordingly, after sizing the solid carbonaceous material particles, the solid carbonaceous material may be pre treated by first forming a mixture of the solid WO 2009/059369 PCT/AU2008/001649 11 carbonaceous material, a catalyst and the diluent in which the catalyst is at least partially soluble. Typically, the ratio of catalyst to solid carbonaceous material will be within a range of about 1 to 20% w/w, as described 5 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 10 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 15 range of about 60 minutes to 480 minutes. In general, the pre-treatment of the solid carbonaceous material may be accomplished in a batch or a continuous operation. Once the pre-treatment has been completed, a desired 20 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 25 described above. The invention will be illustrated in greater detail with reference to the following examples. 30 Example 1 Brown coal (Loy Yang, Table 1) was ground to fine (approximately 300 mesh) particles. 35 Pre-swelling and Catalyst Dispersal WO 2009/059369 PCT/AU2008/001649 12 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 5 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. 10 Donor Solvent Extraction The pre-swollen coal was then mixed with 200 mL tetralin (1,2,3,4-tetrahydronaphtalene) and placed in a 600 mL PARR 15 (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 20 increased to 2650 psi. The reactor was then cooled to room temperature and opened following pressure release. The coal liquefaction products were then analysed. Determination of THF insolubles 25 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 30 through a Buchner funnel with a Whatman's No. 5 filter paper (2.6 pm 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 35 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 WO 2009/059369 PCT/AU2008/001649 13 filter was then reweighed. The residual solid (12.0 g) on the filter paper is the THF insoluble coal fraction. Percentage coal (maf) soluble in THF 5 = (50-12) x 100 50 = 76% 10 The 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. Determination of hexane insolubles (asphaltenes and pre 15 asphaltenes) A portion of the coal liquids filtrate isolated above (5 g) was weighed and mixed with 200 mL of hexane. The mixture was allowed to stand at room temperature for 30 20 minutes, after which it was filtered through a Bchner funnel with a Whatman's No. 5 filter paper using a water pump.. The residual solid (0.2 g) on the filter paper was the hexane insoluble fraction. 25 Weight of coal liquids sample added to hexane = 5 g Weight of insolubles on filter paper = 0.2 g Percentage of hexane solubles in 5 g coal liquids = (0.2/5.0) x 100 = 4% 30 Therefore the combined. weight of pre-asphaltenes and asphaltenes in the coal sample is 2 g. Determination of toluene insolubles (pre-asphaltenes) 35 WO 2009/059369 PCT/AU2008/001649 14 The toluene insolubles were determined using the same procedure as used for the hexane insolubles, except that toluene was used instead of hexane. 5 Weight of sample added to toluene = 5 g Weight of insolubles on filter paper = 0.22 g Percentage of toluene solubles in 5 g coal liquids = (0.22/5.0) x 100 = 0.44% 10 Therefore 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. 15 Results 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 20 volume. The appearance of the coal remains as very fine discrete particles. About 36% of the coal is converted into hexane soluble liquids (oils). 25 Weight % w/w Coal (maf) 50 g THF insolubles 12 g 24.00 Asphaltenes 1.78 g 3.60 Pre-asphaltenes 0.22 g 0.44 Oil (hexane solubles) 36 g - 72.00 Mass Spectroscopy Analysis A sample of the THF soluble extract was analysed by direct 30 injection gas chromatography mass spectrometry (GCMS). The resulting analysis (Figures 1 to 4) shows two major WO 2009/059369 PCT/AU2008/001649 15 peaks that represent the solvents used in the process (i.e. THF and tetralin), however there are a number of peaks representing higher mass molecules (40 to 70 time range) that are coal liquefaction products. Compounds in 5 the coal liquefaction products which were identified by GCMS are listed in Table 2. It is to be understood that, although prior art use and publications may be referred to herein, such reference 10 does not constitute an admission that any of these form a part of the common general knowledge in the art, in Australia or any other country. For the purposes of this specification it will be clearly 15 understood that the word "comprising" means "including but not limited to", and that the word "comprises" has a corresponding meaning. Numerous variations and modifications will suggest 20 themselves to persons skilled in the relevant art, in addition to those already described, without departing from the basic inventive concepts. All such variations and modifications are to be considered within the scope of the present invention, the nature of which is to be 25 determined from the foregoing description.

WO 2009/059369 PCT/AU2008/001649 16 Table 1 Loy Yang Coal Quality Distribution Coal: Loy Yang 1980 Mine Area Weighted 5% 50% 95% Average Proximate Analysis Moisture, % 62.7 59.2 62.7 65.9 Ash, %db 1.4 0.8 1.2 3.9 Volatiles, %db 49.1 51.6 54.3 51.3 Fixed Carbon, %db (Note 1) 49.5 Not applicable Elemental Analysis, %db C 68.4 65.6 68.8 70.7 H 4.9 4.6 4.9 5.2 0 by Diff (Note 2, Note 3) 24.6 Not applicable N 0.5 0.4 0.5 0.6 S (total) 0.4 0.2 0.3 0.7 Specific energy - Gross Dry MJ/kg 26.6 25.1 26.7 27.8 Minerals and Inorganics, % db SiO2 0.34 0.02 0.10 1.41 A1203 0.38 0.02 0.16 1.32 K20 Trace TiO2 Trace FeS2 Trace Fe total 0.13 0.05 0.12 0.25 Fe np 0.13 0.05 0.12 0.25 Ca 0.04 0.01 0.03 0.12 Mg 0.08 0.03 0.06 0.17 Na 0.11 0.04 0.08 0.33 Cl 0.14 0.05 0.10 0.37 Total Mineral (& Inorganic) Matter 1.2 Not applicable Calculated Ash (Note 2) 1.5 Measured Ash 1.4 0.8 1.2 3.9 Ash Composition, % in Ash (Note 2) Si02 22.5 A1203 25.1 K20 0.0 TiO2 0.0 F e203 12.3 Not applicable CaO 3.7 MgO 8.8 Na2O 9.8 S03 17.9 Sum of Components 100.0 WO 2009/059369 PCT/AU2008/001649 17 Inorganic Analysis, % in dry coal Si 0.16 0.01 0.05 0.66 Al 0.19 0.01 0.08 0.65 K Trace Ti Trace Fe 0.13 0.05 0.12 0.25 Ca 0.04 0.01 0.03 0.12 Mg 0.08 0.03 0.06 0.17 Na 0.11 0.04 0.08 0.33 Cl 0.14 0.05 0.10 0.37 Notes: [1] Fixed carbon is a misleading parameter to quote for brown coals, as it is the difference balance after deducting the volatile matter and ash contents from the dry coal weight. However, there is no ash in the coal, only minerals and inorganics, the ash is the residue after combustion of the organic coal substance and includes oxides of the inorganics in the coal and some sulphation of these oxides. [2] 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. [3] 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.

WO 2009/059369 PCT/AU2008/001649 18 Table 2 - Identification of Coal Liquefaction Products by GCMS 07-178 Sample B lab no. 0717802W.D Tentative Identification RT %match area Furan, tetrahydro- 14.1 91 292622 Xylene 26.8 94 609 Phenol 29.8 91 2287 11H-Indene, 2,3-dihydro- 31.9 81 987 Phenol, 2-methyl- 32.3 97 460 Benzene, butyl- 32.5 91 831 Naphthalene, decahydro- 32.6 97 15920 Phenol, 3-methyl- 32.8 97 1909 E-1-phenylbutetene 33.4 95 683 1 H-Indene, 2,3-dihydro-1-methyl- 33.5 93 6487 Naphthalene, decahydro-, cis- 34.0 99 34167 3-Methylene-bicyclo[4.3.0]nonane 34.8 87 6186 Phenol, 3-ethyl- 35.7 91 936 Naphthalene, 1,2,3,4-tetrahydro- 35.8 97 3348051 Naphthalene 36.6 95 512990 Phenol, 2,4,5-trimethyl- 36.8 94 3209 3,6-Dimethyl-1 H-indazole 37.3 72 1596 2-Methyl-1,2,3,4-tetrahydronaphthalene 37.4 94 1526 Benzene, cyclopentyl- 37.6 96 3809 5-Ethylindan 37.8 80 4680 Benzene, 1-pentenyl- 37.9 80 2964 1H-Indene, 2,3-dihydro-4,7-dimethyl- 38.2 97 3072 11H-Indene, 2,3-dihydro-4,6-dimethyl- 38.7 97 833 Naphthalene, 1,2,3,4-tetrahydro-5-methyl- 38.7 95 6063 Tridecane 39.1 96 1439 Naphthalene, 1,2,3,4-tetrahydro-6-methyl- 39.4 95 2914 Naphthalene, 2-methyl- 39.6 95 7990 Naphthalene, 1-methyl- 40.0 94 3767 1-Ethyl- 1,2,3,4-Tetrahydronaphthalene 40.3 91 713 1-Naphthalenol,.1,2,3,4-tetrahydro- 41.0 87 550 Naphthalene, 6-ethyl-1,2,3,4-tetrahydro- 41.1 91 1104 1 (2H)-Naphthalenone, 3,4-dihydro- 41.6 96 4902 Naphthalene, 1-ethyl- 42.1 97 1334 Naphthalene, 2-ethyl- 42.2 93 702 1,2,3,4-tetrahydro-6-isopropylnaphthalene 42.5 72 247 BHT 44.5 98 3519 Furan, 3-phenyl- 44.7 87 541 1,1'-Binaphthalene, 5,5',6,6',7,7',8,8'-octahydro- 56.8 78 3593 Benz[a]anthracene-7,12-dione 57.9 90 8248 2,2'-Binaphthalene, 1,1',2,2',3,3',4,4'-octahydro- 58.6 93 2892 4,5,7,8,9,10-Hexahydrobenzo[A]pyrene 58.9 93 1835 1,2'-Binaphthalene, 1',2',3',4'-tetrahydro- 59.3 90 1175 Benzo[a]pyrene, 4,5-dihydro- 59.7 86 865 4,5,6,7,8,9,9a,10,11, 12-Decahydroperylene 60.6 91 1339

Claims

1. A process for producing a hydrocarbonaceous liquid from a solid carbonaceous material comprising the 5 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 under conditions where at least a portion 10 of the solid carbonaceous material is converted to the hydrocarbonacous liquid; and b) recovering the hydrocarbonaceous liquid.

2. The process according to claim 1, wherein reacting 15 the slurry with supercritical carbon dioxide is performed at a temperature in a range of about.350 "C to about 500 *C.

3. The process according to claim 2, wherein reacting 20 the slurry with supercritical carbon dioxide is performed at a temperature in a range of about 350 *C to about 380 *C.

4. The process according to any one of claims 1 to 2, 25 wherein reacting the slurry with supercritical carbon dioxide. is performed at a pressure in a range of about 500 psi to 3000 psi.

5. The process according to claim 4, wherein reacting 30 the slurry with supercritical carbon dioxide is performed at a pressure in a range of about 500 psi to 1500 psi.

6. The process according to any one of the preceding 35 claims, wherein the catalyst is dissolved or dispersed in a diluent. WO 2009/059369 PCT/AU2008/001649 20

7. The process according to claim 6, wherein the catalyst is at least partially soluble in the diluent. 5

8. The process according to claim 6 or claim 7, wherein the diluent comprises one or more polar solvents and/or aprotic solvents.

9. The process according to claim 8, wherein the diluent 10 comprises water, methanol, ethanol, acetonitrile, dimethylsulfoxide, dimethylformamide, or mixtures of one or more thereof.

10. The process according to any one of the preceding 15 claims, wherein the ratio of catalyst to solid carbonaceous material is in a range of about 1 to 20 % w/w.

11. The process according to any one of the preceding 20 claims, wherein the solid carbonaceous material has a particle size of 200-300 mesh.

12. The process according to any one of the preceding claims, wherein the ratio of hydrogen donor solvent 25 to solid carbonaceous material is in a range of about 1:1 to about 5:1 on a weight basis.

13. The process according to any one of claims 6 to 12, wherein prior to step a), the solid carbonaceous 30 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. 35

14. The process according to claim 13, wherein reacting the mixture with supercritical carbon dioxide is WO 2009/059369 PCT/AU2008/001649 21 performed at a temperature in a range of about 50 *C to 250 *C.

15. The process according to claim 13 or claim 14, 5 wherein reacting the mixture with supercritical carbon dioxide is performed at a pressure in a range of about 500 psi to 3000 psi.

16. The process according to any one of claims 13 to 15, 10 wherein reacting the mixture with supercritical carbon dioxide is performed for a period in a range of about 60 minute to 480 minutes.

17. The process according to any one of claims 6 to 9, 15 wherein pre-treating the solid carbonaceous material is performed as a batch process or a continuous operation.

18. A process for improving the dispersion of a catalyst 20 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. 25

19. The process according to claim 18, wherein reacting the mixture with supercritical carbon dioxide is performed at a temperature in a range of about 50 'C to 250 *C. 30

20. The process according to claim 18 or claim 19, wherein reacting the mixture with supercritical carbon dioxide is performed at a pressure in a range of about 500 psi to 3000 psi. 35

21. The process according to any one of claims 18 to 20, wherein reacting the mixture with supercritical WO 2009/059369 PCT/AU2008/001649 22 carbon dioxide is performed for a period in a range of about 60 minute to 480 minutes.

22. The process according to any one of claims 18 to 21, 5 wherein the catalyst is dissolved or dispersed in the diluent.

23. The process according to claim 22, wherein the catalyst is at least partially soluble in the 10 diluent.

24. The process according to any one of claims 18 to 21, wherein the diluent comprises one or more polar solvents and/or aprotic solvents. 15

25. The process according to claim 24, wherein the diluent comprises water, methanol, ethanol, acetonitrile, dimethylsulfoxide, dimethylformamide, or mixtures of one or more thereof. 20

26. The process according to any one of claims 18 to 25, wherein the ratio of catalyst to solid carbonaceous material is in a range of about 1 to 20 % w/w.

27. The process according to any one of claims 18 to 26, 25 wherein the solid carbonaceous material has a particle size of 200-300 mesh.

28. A process for swelling particles of solid carbonaceous material comprising treating the 30 particles of solid carbonaceous material with supercritical carbon dioxide.

29. The process according to claim 28, wherein treating the particles of solid carbonaceous material with 35 supercritical carbon dioxide is performed at a temperature in a range of about 50 *C to 250 *C. WO 2009/059369 PCT/AU2008/001649 23

30. The process according to claim 28 or claim 29, wherein treating the particles of solid carbonaceous material with supercritical carbon dioxide is performed at a pressure in a range of about 500 psi 5 to 3000 psi.

31. The process according to any one of claims 28 to 30, wherein treating the particles of solid carbonaceous material with. supercritical carbon dioxide is 10 performed for a period in a range of about 60 minute to 480 minutes.

32. A process for producing a hydrocarbonaceous liquid from a solid carbonaceous material comprising the 15 steps of: a. providing a mixture of the solid carbonaceous material, a catalyst, and a diluent and reacting the mixture in the presence of supercritical carbon dioxide; 20 b. reacting the mixture resulting from step a) with a hydrogen donor solvent in the presence of supercritical carbon dioxide under conditions where at least a portion of the solid carbonaceous material is converted to the hydrocarbonaceous 25 liquid.