CA2631916A1 - Catalyst combination and process for direct liquefaction of carbonaceous materials by using the same - Google Patents
Catalyst combination and process for direct liquefaction of carbonaceous materials by using the same Download PDFInfo
- Publication number
- CA2631916A1 CA2631916A1 CA002631916A CA2631916A CA2631916A1 CA 2631916 A1 CA2631916 A1 CA 2631916A1 CA 002631916 A CA002631916 A CA 002631916A CA 2631916 A CA2631916 A CA 2631916A CA 2631916 A1 CA2631916 A1 CA 2631916A1
- Authority
- CA
- Canada
- Prior art keywords
- catalyst combination
- coal
- iodine
- carbonaceous material
- solvent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
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- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 70
- 239000003054 catalyst Substances 0.000 title claims abstract description 67
- 238000000034 method Methods 0.000 title claims abstract description 51
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims abstract description 47
- 239000011630 iodine Substances 0.000 claims abstract description 47
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 46
- 239000000126 substance Substances 0.000 claims abstract description 36
- TXKMVPPZCYKFAC-UHFFFAOYSA-N disulfur monoxide Inorganic materials O=S=S TXKMVPPZCYKFAC-UHFFFAOYSA-N 0.000 claims abstract description 32
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000002904 solvent Substances 0.000 claims description 47
- 239000003245 coal Substances 0.000 claims description 40
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 36
- 239000000203 mixture Substances 0.000 claims description 31
- 239000003077 lignite Substances 0.000 claims description 22
- 239000000852 hydrogen donor Substances 0.000 claims description 20
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 claims description 18
- 239000003921 oil Substances 0.000 claims description 16
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 claims description 16
- 239000007789 gas Substances 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 14
- 150000002430 hydrocarbons Chemical group 0.000 claims description 10
- 239000004058 oil shale Substances 0.000 claims description 10
- 239000011269 tar Substances 0.000 claims description 10
- 239000002802 bituminous coal Substances 0.000 claims description 9
- LBUJPTNKIBCYBY-UHFFFAOYSA-N 1,2,3,4-tetrahydroquinoline Chemical compound C1=CC=C2CCCNC2=C1 LBUJPTNKIBCYBY-UHFFFAOYSA-N 0.000 claims description 8
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 claims description 8
- BIZCJSDBWZTASZ-UHFFFAOYSA-N diiodine pentaoxide Chemical compound O=I(=O)OI(=O)=O BIZCJSDBWZTASZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- RHZUVFJBSILHOK-UHFFFAOYSA-N anthracen-1-ylmethanolate Chemical compound C1=CC=C2C=C3C(C[O-])=CC=CC3=CC2=C1 RHZUVFJBSILHOK-UHFFFAOYSA-N 0.000 claims description 6
- 239000003830 anthracite Substances 0.000 claims description 6
- 239000003208 petroleum Substances 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 6
- 150000001454 anthracenes Chemical class 0.000 claims description 5
- 238000004523 catalytic cracking Methods 0.000 claims description 5
- 239000003345 natural gas Substances 0.000 claims description 5
- 239000003415 peat Substances 0.000 claims description 5
- 239000011541 reaction mixture Substances 0.000 claims description 5
- 239000003476 subbituminous coal Substances 0.000 claims description 5
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 claims description 4
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 claims description 4
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims description 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- BYBPEZLZCGOWIS-UHFFFAOYSA-N perhydropyrene Chemical compound C1CC2CCCC(CC3)C2C2C3CCCC21 BYBPEZLZCGOWIS-UHFFFAOYSA-N 0.000 claims description 4
- 238000004064 recycling Methods 0.000 claims description 4
- YMEKEHSRPZAOGO-UHFFFAOYSA-N boron triiodide Chemical compound IB(I)I YMEKEHSRPZAOGO-UHFFFAOYSA-N 0.000 claims description 3
- 229910000450 iodine oxide Inorganic materials 0.000 claims description 3
- XZXYQEHISUMZAT-UHFFFAOYSA-N 2-[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenol Chemical compound CC1=CC=C(O)C(CC=2C(=CC=C(C)C=2)O)=C1 XZXYQEHISUMZAT-UHFFFAOYSA-N 0.000 claims description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- -1 alkaline earth metal iodates Chemical class 0.000 claims description 2
- 229910001619 alkaline earth metal iodide Inorganic materials 0.000 claims description 2
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 2
- 229940107816 ammonium iodide Drugs 0.000 claims description 2
- ZRDJERPXCFOFCP-UHFFFAOYSA-N azane;iodic acid Chemical compound [NH4+].[O-]I(=O)=O ZRDJERPXCFOFCP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052788 barium Inorganic materials 0.000 claims description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052790 beryllium Inorganic materials 0.000 claims description 2
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052792 caesium Inorganic materials 0.000 claims description 2
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 239000011575 calcium Substances 0.000 claims description 2
- ICIWUVCWSCSTAQ-UHFFFAOYSA-N iodic acid Chemical class OI(=O)=O ICIWUVCWSCSTAQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- 229910001511 metal iodide Inorganic materials 0.000 claims description 2
- AFSVSXMRDKPOEW-UHFFFAOYSA-N oxidoiodine(.) Chemical compound I[O] AFSVSXMRDKPOEW-UHFFFAOYSA-N 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 229910052701 rubidium Inorganic materials 0.000 claims description 2
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 229910052712 strontium Inorganic materials 0.000 claims description 2
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 description 20
- 239000000725 suspension Substances 0.000 description 15
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 12
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 239000000047 product Substances 0.000 description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 10
- 239000012263 liquid product Substances 0.000 description 9
- 239000002245 particle Substances 0.000 description 9
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 239000012265 solid product Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 229910001873 dinitrogen Inorganic materials 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000000921 elemental analysis Methods 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 235000009518 sodium iodide Nutrition 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 238000000944 Soxhlet extraction Methods 0.000 description 2
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 2
- 239000003426 co-catalyst Substances 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- OKJPEAGHQZHRQV-UHFFFAOYSA-N Triiodomethane Natural products IC(I)I OKJPEAGHQZHRQV-UHFFFAOYSA-N 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- YCOXTKKNXUZSKD-UHFFFAOYSA-N as-o-xylenol Natural products CC1=CC=C(O)C=C1C YCOXTKKNXUZSKD-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910000085 borane Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910000043 hydrogen iodide Inorganic materials 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- SNHMUERNLJLMHN-UHFFFAOYSA-N iodobenzene Chemical compound IC1=CC=CC=C1 SNHMUERNLJLMHN-UHFFFAOYSA-N 0.000 description 1
- OZDMLJPVUZSCAP-UHFFFAOYSA-N iodoborane Chemical class IB OZDMLJPVUZSCAP-UHFFFAOYSA-N 0.000 description 1
- HVTICUPFWKNHNG-UHFFFAOYSA-N iodoethane Chemical compound CCI HVTICUPFWKNHNG-UHFFFAOYSA-N 0.000 description 1
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- NALMPLUMOWIVJC-UHFFFAOYSA-N n,n,4-trimethylbenzeneamine oxide Chemical compound CC1=CC=C([N+](C)(C)[O-])C=C1 NALMPLUMOWIVJC-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052756 noble gas Inorganic materials 0.000 description 1
- JLKDVMWYMMLWTI-UHFFFAOYSA-M potassium iodate Chemical compound [K+].[O-]I(=O)=O JLKDVMWYMMLWTI-UHFFFAOYSA-M 0.000 description 1
- 239000001230 potassium iodate Substances 0.000 description 1
- 235000006666 potassium iodate Nutrition 0.000 description 1
- 229940093930 potassium iodate Drugs 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011697 sodium iodate Substances 0.000 description 1
- 235000015281 sodium iodate Nutrition 0.000 description 1
- 229940032753 sodium iodate Drugs 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 239000003039 volatile agent Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
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
- C10G1/08—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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
-
- 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
- C10G1/086—Characterised by the catalyst used
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/08—Halides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/138—Halogens; Compounds thereof with alkaline earth metals, magnesium, beryllium, zinc, cadmium or mercury
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/19—Catalysts containing parts with different compositions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/27—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a liquid or molten state
-
- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1025—Natural gas
-
- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/40—Characteristics of the process deviating from typical ways of processing
- C10G2300/44—Solvents
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The present invention relates to a catalyst combination and a process for direct liquefaction of carbonaceous materials by using the same, in particular, to a catalyst combination comprising an iodine-containing substance and a sulfur oxide species and a process for direct liquefaction of carbonaceous materials by using the catalyst combination.
Description
Catalyst combination and process for direct liquefaction of carbonaceous materials by using the same CROSS REFERENCE
The present invention claims the priority benefit of Chinese Patent Application No.200710201127.X, which has a filling date of July 19, 2007 and is entirely incorporated herein by reference.
FIELD OF INVENTION
The present invention relates to a catalyst combination and a process for direct liquefaction of carbonaceous materials by using the same, in particular, to a catalyst combination comprising an iodine-containing substance and a sulfur oxide species, and a process for direct liquefaction of a carbonaceous material by using the catalyst combination.
BACKGROUND OF THE INVENTION
The prospect that the world petroleum reserves will be depleted within the next several decades has caused the price of oil to escalate. Coal is a raw material of great importance and an abundant natural source. Thus, the coal liquefaction for production of liquid fuels and chemicals might become economically competitive.
Heretofore, a large number of catalysts have been . identified as useful in processes for direct liquefaction of carbonaceous materials. For example, metal sulfides and oxides and mixtures thereof have been particularly useful as catalysts in such processes.
It has also been proposed to use iodine to enhance the hydroconversion of carbonaceous materials such as coal in thermal operations. For example, Maa et al disclosed in United States Patent 4824558 that iodine is added directly as iodine, hydrogen iodine or as a precursor which decomposes to yield either iodine or hydrogen iodide, and the hydroconversion using iodine was accomplished in the presence of hydrogen.
Haenel, et al., in Angew. Chem. Int. Ed., Vol. 45 (2006), had developed a method of converting high-rank bituminous coals by preceding hydrogenation with homogeneous borane or iodine catalyst. It was shown that iodoboranes and iodine could be used as homogeneous catalysts to hydrogenate high-rank bituminous coals, including anthracite, resulting in a strong increase of the aliphatic at the expense of the aromatic structures of these coals. However, the product obtained by stirring a suspension of a bituminous coal in solvent together with catalysts was still a solid.
So far, most of existing processes for direct liquefaction of coal utilize molecular hydrogen at high pressure, so that the considerable expense of hydrogen production is one of the significant limitations for commercial application of these coal liquefaction processes. Sundaram, et al disclosed in U.S. Pat.
No.4,687,570 that methane was directly used in coal liquefaction, but they did not use any catalyst in coal liquefaction.
Thus, there are still demands of novel catalyst systems and processes for direct liquefaction of carbonaceous materials such as coal.
SUMMARY OF THE INVENTION
In one aspect, the present invention provides a catalyst combination for direct liquefaction of carbonaceous materials, in which the catalyst combination comprises:
a) An iodine-containing substance, and b) A sulfur oxide species.
In another aspect, the present invention provides a method of using a catalyst combination for direct liquefaction of carbonaceous materials, in which the catalyst combination comprises:
a) An iodine-containing substance, and b) A sulfur oxide species.
In further another aspect, the present invention provides a process for liquefaction of carbonaceous materials, comprising:
(1) providing a catalyst combination comprising a) an iodine-containing substance, and b) a sulfur oxide species;
(2) contacting a carbonaceous material with a hydrogen-donor in the presence of the catalyst combination optionally in a solvent under a temperature between 250 C and 750 C and a pressure between 0.2MPa and 20MPa.
DETAILED DESCRIPTION OF THE INVENTION
The term "catalyst combination" used herein, in suitable conditions, may also be replaced by "catalyst system" or "catalyst composition", and means a combination comprising two or more components which exhibit catalytic activity when they are used together in direct liquefaction of a carbonaceous material.
In some cases, at least one of the components may be in its original form, and if any, the residual component(s) may form one or more solutions and/or mixtures such as suspensions. In some other cases, all components may form a solution or a mixture.
The term "liquefaction of carbonaceous material" used herein means a process in which a carbonaceous material is treated with suitable substances, such as a hydrogen-donor and a catalyst combination in accordance with the present invention, under suitable conditions to convert at least a part of the carbonaceous material into liquid and/or gaseous products.
The present invention claims the priority benefit of Chinese Patent Application No.200710201127.X, which has a filling date of July 19, 2007 and is entirely incorporated herein by reference.
FIELD OF INVENTION
The present invention relates to a catalyst combination and a process for direct liquefaction of carbonaceous materials by using the same, in particular, to a catalyst combination comprising an iodine-containing substance and a sulfur oxide species, and a process for direct liquefaction of a carbonaceous material by using the catalyst combination.
BACKGROUND OF THE INVENTION
The prospect that the world petroleum reserves will be depleted within the next several decades has caused the price of oil to escalate. Coal is a raw material of great importance and an abundant natural source. Thus, the coal liquefaction for production of liquid fuels and chemicals might become economically competitive.
Heretofore, a large number of catalysts have been . identified as useful in processes for direct liquefaction of carbonaceous materials. For example, metal sulfides and oxides and mixtures thereof have been particularly useful as catalysts in such processes.
It has also been proposed to use iodine to enhance the hydroconversion of carbonaceous materials such as coal in thermal operations. For example, Maa et al disclosed in United States Patent 4824558 that iodine is added directly as iodine, hydrogen iodine or as a precursor which decomposes to yield either iodine or hydrogen iodide, and the hydroconversion using iodine was accomplished in the presence of hydrogen.
Haenel, et al., in Angew. Chem. Int. Ed., Vol. 45 (2006), had developed a method of converting high-rank bituminous coals by preceding hydrogenation with homogeneous borane or iodine catalyst. It was shown that iodoboranes and iodine could be used as homogeneous catalysts to hydrogenate high-rank bituminous coals, including anthracite, resulting in a strong increase of the aliphatic at the expense of the aromatic structures of these coals. However, the product obtained by stirring a suspension of a bituminous coal in solvent together with catalysts was still a solid.
So far, most of existing processes for direct liquefaction of coal utilize molecular hydrogen at high pressure, so that the considerable expense of hydrogen production is one of the significant limitations for commercial application of these coal liquefaction processes. Sundaram, et al disclosed in U.S. Pat.
No.4,687,570 that methane was directly used in coal liquefaction, but they did not use any catalyst in coal liquefaction.
Thus, there are still demands of novel catalyst systems and processes for direct liquefaction of carbonaceous materials such as coal.
SUMMARY OF THE INVENTION
In one aspect, the present invention provides a catalyst combination for direct liquefaction of carbonaceous materials, in which the catalyst combination comprises:
a) An iodine-containing substance, and b) A sulfur oxide species.
In another aspect, the present invention provides a method of using a catalyst combination for direct liquefaction of carbonaceous materials, in which the catalyst combination comprises:
a) An iodine-containing substance, and b) A sulfur oxide species.
In further another aspect, the present invention provides a process for liquefaction of carbonaceous materials, comprising:
(1) providing a catalyst combination comprising a) an iodine-containing substance, and b) a sulfur oxide species;
(2) contacting a carbonaceous material with a hydrogen-donor in the presence of the catalyst combination optionally in a solvent under a temperature between 250 C and 750 C and a pressure between 0.2MPa and 20MPa.
DETAILED DESCRIPTION OF THE INVENTION
The term "catalyst combination" used herein, in suitable conditions, may also be replaced by "catalyst system" or "catalyst composition", and means a combination comprising two or more components which exhibit catalytic activity when they are used together in direct liquefaction of a carbonaceous material.
In some cases, at least one of the components may be in its original form, and if any, the residual component(s) may form one or more solutions and/or mixtures such as suspensions. In some other cases, all components may form a solution or a mixture.
The term "liquefaction of carbonaceous material" used herein means a process in which a carbonaceous material is treated with suitable substances, such as a hydrogen-donor and a catalyst combination in accordance with the present invention, under suitable conditions to convert at least a part of the carbonaceous material into liquid and/or gaseous products.
In certain embodiments of the catalyst combination, the iodine-containing substance is any suitable iodine-containing substance, such as iodine element, iodine oxide, iodic acid anhydride, ammonium iodide, alkaline metal iodides, alkaline earth metal iodides, ammonium iodate, alkaline metal iodates, alkaline earth metal iodates, boron iodide, organic iodine-containing compounds, and mixtures thereof, wherein the alkaline metal can be lithium, sodium, potassium, rubidium, or cesium, and the alkaline earth metal can be beryllium, magnesium, calcium, strontium, or barium, and wherein the organic iodine-containing compounds may be hydrocarbonyl iodide such as iodobenzene, iodomethane, iodoethane. In some cases, the iodine-containing substance is in the form of particles having an average diameter of 1-1000pm, preferably 10-500Nm, more preferably 50-250pm, most preferably 70-100Nm.
In some embodiments of the catalyst combination, the sulfur oxide species is any suitable sulfur oxide species such as sulfur trioxide, sulfur dioxide, oleum, concentrated sulfuric acid, and mixtures thereof. In some cases, the concentration of sulfur trioxide in oleum is 20-60wt%, and the sulfur trioxide is in the form of gas or solid.
In some embodiments, the catalyst combination can be, for example, a combination selected from potassium iodide/oleum, potassium iodide/sulfur trioxide, sodium iodide/oleum, sodium iodide/sulfur trioxide, iodic anhydride/oleum, iodic anhydride/sulfur trixoide, iodine/oleum, and iodine/sulfur trioxide.
In certain embodiments of the present invention, the catalyst combination may further comprise a suitable solvent. In some cases, the iodine-containing substance and/or the sulfur oxide species may be mixed with the solvent to form one or more solutions and/or mixtures such as suspensions, slurries or powders before they are used as a catalyst in a process for liquefaction of carbonaceous materials. In some other cases, at least one of the iodine-containing substance, the sulfur oxide species and the solvent may be mixed with others only when they are used as a catalyst in a process for liquefaction of carbonaceous materials.
Examples of such solvent may be hydroaromatic solvents. Some specific examples of the solvent include tetralin, tetrahydroquinoline, piperidine, indoline, perhydropyrene, pyrolidine, as well as hydrogenated anthracene oil, hydrogenated coal liquids, catalytic cracking residual oil, heavy hydrocarbon residues, and mixtures thereof.
In certain embodiments of the present invention, the catalyst combination may further comprise a carbonaceous material. In some cases, the iodine-containing substance and/or the sulfur oxide species and/or optionally the solvent may be mixed with the carbonaceous material to form one or more solutions and/or mixtures such as suspensions, slurries or powders before they are used in a process for liquefaction of carbonaceous materials. In some other cases, at least one of the iodine-containing substance, the sulfur oxide species, the solvent and the carbonaceous material may be mixed with others only when they are used in a process for liquefaction of carbonaceous materials. The carbonaceous material can be any suitable carbonaceous material that needs to be liquefied or contains at least a portion to be liquefied, such as coal including bituminous coal, brown coal, hard coal, sub-bituminous coal, anthracite coal, peat and lignite, oil shale, petroleum, tar sands, oil shale, and man-made residual oils, tars and heavy hydrocarbon residues, and mixtures thereof. In some cases, the carbonaceous material may be in the form of particles having an average diameter of 1-5000pm, preferably 10-500pm, more preferably 50-250pm, most preferably 70-100Nm. In some cases, the moisture of carbonaceous material is less than 10%, preferably iess than 5%, more preferably less than 2%.
In certain embodiments of the present invention, if appropriate, two or more or all components of the catalyst combination may form a solution or a mixture such as suspension, slurry or powder, while other components, if any, may be in their original forms individually or form other mixtures and/or solutions. In some cases, each of mixtures or solutions or components in the catalyst combination may be kept individually during manufacture, transportation and/or storage, for example, they may be packaged in different containers individualiy or in different chambers of one or more containers. This may be advantageous under some situations to avoid, if any, for example, undesired interactions between components before they are used as a catalyst combination, or to facilitate the manufacture, transportation and/or storage of such catalyst combination. In some embodiments, all components may be in their original forms individually and kept individually during manufacture, transportation and/or storage. However, in any above case, all components of the catalyst combination are considered as a whole and are used together at the same time or in any suitable order in a process for liquefaction of carbonaceous materials. In some embodiments, the catalyst combination is a solution or a mixture, which comprises an iodine-containing substance and a sulfur oxide species. In some other cases, when two or more of the components in the combination are mixed together, they may have, if appropriate, a physical or chemical interaction between each other, providing that the interaction does not significantly interfere the liquefaction of carbonaceous materials.
In the present invention, the ratio of components in the catalyst combination may be determined according to actual conditions and requirements. In some embodiments, the weight ratio of iodine-containing substance : sulfur oxide species is 0.2-10 : 0.5-20, preferably 1-5 : 5-15. In the case that the catalyst combination comprises a solvent and/or a carbonaceous material, the weight ratio of iodine-containing substance : sulfur oxide species : solvent : carbonaceous material is 0.2-10 : 0.5-20 : 0-1000 : 0-100, preferably 1-5 : 5-15 : 0-200 0-50, more preferably 1-2 : 6-10 : 0-150 : 0-50.
In some embodiments of the present invention, the iodine-containing substance and/or sulfur oxide species used in the process for liquefaction of carbonaceous materials may be at least partially or totally provided by a catalyst combination as described hereinabove. For example, in some embodiments, the process may use only the catalyst combination in accordance with the present invention to provide the needed iodine-containing substance and sulfur oxide species, while in other embodiments, the process may use the catalyst combination described herein to provide a portion of iodine-containing substance and a portion of sulfur oxide species. Similarly, the carbonaceous materials and the solvent used in the process may be partially or totally provided by the catalyst combination in accordance with the present invention as well. In some embodiments, besides those contained in the catalyst combination as described herein, the process may further use additional same or different iodine-containing substance, sulfur oxide species, solvent and/or carbonaceous material as described hereinabove.
In some embodiments of the present invention, the carbonaceous materials to be liquefied in the process of the present invention may be any suitable carbonaceous materials that needs to be liquefied or contains at least a portion to be liquefied, and examples of the carbonaceous materials may include coal such as bituminous coal, brown coal, hard coal, sub-bituminous coal, anthracite coal, peat and lignite, oil shale, petroleum, tar sands, oil shale, man-made residual oils, tars, heavy hydrocarbon residues, and mixtures thereof.
In some embodiments of the present invention, the solvent used in the process may serve as a liquid vehicle and/or a hydrogen-donor. Examples of such solvent may comprise hydroaromatic solvents, such as tetralin, tetrahydroquinoline, piperidine, indoline, perhydropyrene, pyrolidine, as well as hydrogenated anthracene oil, hydrogenated coal liquids, catalytic cracking residual oil, heavy hydrocarbon residues, and mixtures thereof.
In some embodiments of the process, the hydrogen-donor may be a hydrogen-containing compound or a mixture comprising such compound, and the examples of hydrogen-donor may include natural gas, coal-bed gas, methane, ethane, coal oven gas, hydrogen gas, or a mixture thereof. In some cases, the gas may further comprise hydrogen gas and/or an inert gas such as noble gas and nitrogen gas. In some embodiments, natural gas, coal-bed gas and/or coal oven gas is used directly, or is used to replace 50-100% by volume of the methane in a mix consisting of methane and hydrogen in a ratio of 99:1 - 1:99.
In another embodiment, natural gas or methane is solely used as the hydrogen-donor.
In the process of the present invention, the components of iodine-containing substance, sulfur oxide species, solvent and carbonaceous material may be added in a reactor simultaneously or in sequence by any order.
In the present invention, the ratio of components used in the process may be determined according to actual conditions and requirements. In some embodiments, the weight ratio of iodine-containing substance : sulfur oxide species : solvent : carbonaceous material in the process is 0.2-10 : 0.5-20 50-1000 : 10-100, preferably 1-5 : 5-15 : 70-200 : 100, more preferably 1-2 6-10 : 100-150 : 100.
In some embodiments of the process, the hydrogen-donor is provided in a gaseous form with a cold pressure of 0.1 -10MPa, preferably 2-9MPa, more preferably 3-5MPa.
In some embodiments of the process, the carbonaceous material contacts with the hydrogen-donor in the solvent under a temperature between 250 C and 750 C, preferably between 280 C and 500 C, more preferably between 280 C and 420 C, and a pressure between 0.2MPa and 20MPa, preferably between 5MPa and 15MPa, more preferably between 7MPa and 12MPa for a time period of 0.5-24 hours, preferably 0.5-12 hours, more preferably 0.5-4 hours.
In some embodiments of the present invention, without limitation of any theory, it is believed that the iodine-containing substance may serve as a primary catalyst, the sulfur oxide species may serve as a co-catalyst, and the solvent may serve as both a vehicle as well as a reactant such as a hydrogen-donor, and the presence of the hydrogen-donor solvent together with the hydrogen-donor gas such as methane may increase the yield of desired liquid and gaseous hydrocarbons during the liquefaction of carbonaceous materials.
In some embodiments of the present invention, the iodine-containing substance, sulfur oxide species, solvent and/or carbonaceous material may be used in the form of a solid-liquid or liquid-liquid reaction mixture and fed into a reaction vessel and pressurized to an elevated pressure. In some cases, the reaction mixture may be preheated up to 100 C, preferably to 80-90 C, before introducing it into a reaction vessel. When the contents of the reaction vessel are heated to the reaction temperature, the reaction occurs between the carbonaceous, solvent and hydrogen-donor gas such as methane. This results in the formation of new and useful liquid products and gaseous products.
In some embodiments of the present invention, the process may further comprise: (3) separating a liquefaction product from a reaction mixture after the liquefaction.
In some embodiments of the present invention, the process may further comprise: (4) directly recycling the residue after the separation, or separating the iodine-containing substance, sulfur oxide species, solvent and/or carbonaceous material from the residue and optionally recycling at least one of them.
In some embodiments of the present invention, the liquefaction product can be any desired liquid and gaseous products which could be separated from a reaction mixture after liquefaction, in which the examples of suitable separation means may comprise centrifugation, distillation, vaporization, filtration, extraction and so on. In some cases, at least a part of the residue after the separation may be directly recycled without any further separation. In some other cases, the residue may be further separated to obtain the iodine-containing substance, sulfur oxide species, solvent and/or carbonaceous material, and at least one of them may be recycled to replace at least partial or total iodine-containing substance, sulfur oxide species, solvent and/or carbonaceous material used in the process for liquefaction of carbonaceous materials. In some other cases, the liquid and gaseous products obtained by the separation may also be further processed to obtain a solvent and/or hydrogen-donor gas which can be used as solvent and/or hydrogen-donor gas in the next turn of process for liquefaction of carbonaceous materials.
EXAMPLES
Although the present invention is described in terms of specific materials and process steps, it will be clear to one skilled in the art that various changes and modifications may be made in accordance with the invention described in the accompanying claims.
The following examples are presented merely by way of illustration and are not intended to limit the present invention beyond that defined in the accompanying claims.
In the following examples, Inner Mongolia lignite, Shanxi bituminous coal are ground to a diameter of less than 0.1 mm, classified as <160mesh (about 100 micrometers) and <200mesh (about 75 micrometers) respectively, dried under vacuum at 100 C for 24hrs, and used as feedstock. The results of elemental analyses of these raw coals are summarized in Table 1.
Table 1. Elemental analyses of raw coals Inner Mongolia Shanxi bituminous lignite coal coal Elemental analysis, %, dmmf C 61.1 77.86 H 2.79 4.32 S(total) 1.60 1.31 O(by difference) 8.06 8.16 H/C 0.55 0.67 Proximate analysis, %
Moisture, as received 5.94 2.47 Fixed carbon, dry 53.72 64.76 Volatile matter, dry 20.50 27.67 Calorific value, KJ/kg 23590 31480 In the following examples, the solid and liquid reaction products are analyzed by solvent fractionation using a series of extraction solvents, and the amount of gaseous products are determined by weighing the gases in the reactor before and after the gaseous products are released from the reactor.
The liquid products are fractionated by using a series of solvents into a hexane-soluble fraction (HXs); a tetrahydrofuran(THF)-soluble, hexane-insoluble fraction; and a THF-insoluble fraction which is also defined as an insoluble organic matter (IOM) that is moisture and ash free (maf). The amount of each of the fractions, except for the HXs, is determined by weighing the fraction after the solvent is evaporated off. The HXs is determined by a different way so that all losses, including those due to the escape of volatiles, are counted in this fraction.
Thus, the conversion refers to a weight conversion of carbonaceous material, and is calculated by using the following equation.
%convers;on = 1-910M x 100 g maf Wherein %conversion represents the weight convention of the carbonaceous material; gioM represents the weight of THF-insoluble organic matter after the reaction, which is calculated by the following equation: g,oM = (the weight of the THF-insoluble fraction after the reaction) - (the weight of moisture and ash in the original carbon carbonaceous material); and gmaf represents the weight of the moisture and ash free carbonaceous material, which is calculated by the equation:
gn,af = (the weight of the original carbonaceous material) - (the weight of moisture and ash in the original carbon carbonaceous material).
The HS yield refers to a weight yield of the n-hexane-soluble liquid and gaseous products, and is calculated by using the following equation.
HS yield (wt%) = [(the weight of the original carbon carbonaceous material) +
(the weight loss of the hydrogen-donor) - (the weight of the n-hexane-insoluble fraction)]/(the weight of the original carbon carbonaceous material) Example 1 About 150 grams of tetralin as solvent were added to 75 grams of particulate Inner Mongolia lignite coal having a particle size of less than 100 micrometers to form a suspension A. About 0.35 gram of potassium iodide and 10 grams of 20%
oleum were mixed with the suspension A, which was then loaded in an autoclave with a capacity of 1000-m1 for direct liquefaction.
The air of the autoclave was firstly replaced by nitrogen for three times, and then gaseous methane (cold pressure of 5.OMPa) was introduced into the autoclave. The autoclave was then sealed and heated to 300 C for 1 h under an autogenous pressure (10MPa) with vigorous stirring (400rpm).
After the end of reaction, the gaseous, liquid and solid products of coal liquefaction were recovered from the autoclave by washing out with tetrahydrofuran (THF). After THF was removed by evaporation at 80 C under vacuum for 12 hours, the resultant residue was extracted with n-hexane by Soxhlet Extraction for 24 hours and dried at a temperature of 80 C under vacuum for 12 hours to obtain an n-hexane insoluble fraction, then the n-hexane insoluble fraction was further extracted with THF by Soxhlet extraction for 24 hours and dried at a temperature of 80 C under vacuum for 24 hours to obtain a THF-insoluble fraction. The conversion and HS yield were calculated in accordance with the above equations and the results were shown in Table 2.
Example 2 About 75 grams of hydrogenated anthracene oil as solvent were added to 75 grams of particulate Inner Mongolia lignite coal having a particle size of less than 75 micrometers to form a suspension B. About 3.75 grams of sodium iodide and 15 grams of 40% oleum were mixed with suspension B, and then the mixture was loaded in an autoclave with a capacity of 1000-m1 for direct liquefaction.
The air of the autoclave was firstly replaced by nitrogen gas for three times, and then gaseous methane (cold pressure of 2.OMPa) was introduced into the autoclave. The autoclave was then sealed and heated to 380 C for 4 h under autogenous pressure (about 7MPa) with vigorous stirring (400rpm).
After the end of reaction, the gaseous, liquid and solid products of coal liquefaction were treated as in Example 1. The results of Example 2 are shown in Table 2.
Example 3 About 300 grams of catalytic cracking residual oil as solvent were added to 75 grams of particulate Shanxi bituminous coal having a particle size of less than 100 micrometers to form a suspension C. About 0.15 grams of boron triiodide and 3.75 grams of 60% oleum were mixed with suspension C, and then the mixture are subjected to direct liquefaction in an autoclave with capacity of 1000-m1.
The air of the autoclave was firstly replaced by nitrogen gas for three times, and then gaseous methane (cold pressure of 4.OMPa) was introduced to the autoclave. The autoclave was then sealed and heated to 420 C for 3 h under autogenous pressure (9 MPa) with vigorous stirring (400rpm).
After the reaction, the gaseous, liquid and solid products of coal liquefaction were treated as in Example 1. The results of Example 3 are shown in Table 2.
Example 4 About 500 grams of tetralin as solvent were added to 75 grams of particulate Shanxi bituminous coal having a particle size of less than 75 micrometers to form a suspension D. About 7.5 grams of potassium iodate, and 11.25 grams of 50%
oleum were mixed with suspension D, and then the mixture was subjected to direct liquefaction in an autoclave of 1000-m1 capacity.
The air of the autoclave was firstly replaced by nitrogen gas for three times, and then gaseous natural gas (cold pressure of 10 MPa) was introduced to the autoclave. The autoclave was then sealed and heated to 280 C for 2 h under autogenous pressure (12 MPa) with vigorous stirring (400rpm).
After the reaction, the gaseous, liquid and solid products of coal liquefaction were treated as in Example 1. The results of Example 4 are shown in Table 2.
Example 5 About 250 grams of a heavy hydrocarbon residue as solvent were added to 75 grams of particulate Inner Mongolia lignite coal having a particle size less than 100 micrometers to form a suspension E, in which the heavy hydrocarbon residue was distilled from the liquid product of Example 1 and had a boiling point range of about 350-400 C. About 0.75 grams of sodium iodate and 0.75 grams of solid sulfur trioxide were mixed with suspension E, and then the mixture was subjected to direct liquefaction in an autoclave of 1000-m1 capacity.
The air of the autoclave was firstly replaced by nitrogen gas for three times, and then gaseous methane (cold pressure of 3.0 MPa) was introduced to the autoclave. The autoclave was then heated to 330 C for 0.5 h under autogenous pressure (7.5 MPa) with vigorous stirring (400rpm).
After the reaction, the gaseous, liquid and solid products of coal liquefaction were treated as in Example 1. The results of Example 5 are shown in table 2.
Example 6 The procedure of Example 1 was followed, except 0.1 gram of iodine and 0.25 gram of diiodine pentoxide instead of 0.35 gram of potassium iodide were used in Example 6.
After the reaction, the gaseous, liquid and solid products of coal liquefaction were treated as in Example 1. The results of Example 6 are shown in Table 2.
Table 2. Results of Examples 1-6 Run Coal Particle Conversion HS yield size (pm) (wt%) (wt%) Example 1 Lignite <100 47.39 37.03 Example 2 Lignite <75 54.6 37.14 Example 3 Bituminous <100 55.95 37.19 Example 4 Bituminous <75 56.33 37.74 Example 5 Lignite <100 57.5 45.53 Example 6 lignite <100 53.3 40.26 Comparative Examples 1~5 The comparative examples 1-5 were conducted respectively under the same conditions of Examples 1-5, except that no catalyst and co-catalyst was used in the comparative examples 1-5. The results of the comparative examples 1-5 are shown in Table 3.
Table 3. Results of Comparative Examples 1-5 Run Coal Particle Conversion HS yield size (pm) (wt%) (wt%) Comparative Example 1 Lignite <100 32.49 25.13 Comparative Example 2 Lignite <75 35.5 30.05 Comparative Example 3 Bituminous <100 37.87 29.2 Comparative Example 4 Bituminous <75 33.33 28.95 Comparative Example 5 Lignite <100 34.85 32.23 It can be seen from the above examples and comparative examples that the catalyst combination in accordance with the present invention exhibited significant effects in direct liquefaction of carbonaceous materials. For example, when the catalyst combination of the present invention was used, the conversion and HS
yield increased significantly. It was also indicated that the direct liquefaction of carbonaceous materials by using the catalyst of the present invention could be implemented by using only methane as hydrogen-donor, rather than by using a hydrogen product such as hydrogen gas or a hydrogen-containing gas.
By reading the present invention, those skilled in the art would understand that the present invention is not intended to be limited by what is disclosed in the examples, and any modifications and variants without departing from the general concept of the present invention fall within the scope of the present invention.
In some embodiments of the catalyst combination, the sulfur oxide species is any suitable sulfur oxide species such as sulfur trioxide, sulfur dioxide, oleum, concentrated sulfuric acid, and mixtures thereof. In some cases, the concentration of sulfur trioxide in oleum is 20-60wt%, and the sulfur trioxide is in the form of gas or solid.
In some embodiments, the catalyst combination can be, for example, a combination selected from potassium iodide/oleum, potassium iodide/sulfur trioxide, sodium iodide/oleum, sodium iodide/sulfur trioxide, iodic anhydride/oleum, iodic anhydride/sulfur trixoide, iodine/oleum, and iodine/sulfur trioxide.
In certain embodiments of the present invention, the catalyst combination may further comprise a suitable solvent. In some cases, the iodine-containing substance and/or the sulfur oxide species may be mixed with the solvent to form one or more solutions and/or mixtures such as suspensions, slurries or powders before they are used as a catalyst in a process for liquefaction of carbonaceous materials. In some other cases, at least one of the iodine-containing substance, the sulfur oxide species and the solvent may be mixed with others only when they are used as a catalyst in a process for liquefaction of carbonaceous materials.
Examples of such solvent may be hydroaromatic solvents. Some specific examples of the solvent include tetralin, tetrahydroquinoline, piperidine, indoline, perhydropyrene, pyrolidine, as well as hydrogenated anthracene oil, hydrogenated coal liquids, catalytic cracking residual oil, heavy hydrocarbon residues, and mixtures thereof.
In certain embodiments of the present invention, the catalyst combination may further comprise a carbonaceous material. In some cases, the iodine-containing substance and/or the sulfur oxide species and/or optionally the solvent may be mixed with the carbonaceous material to form one or more solutions and/or mixtures such as suspensions, slurries or powders before they are used in a process for liquefaction of carbonaceous materials. In some other cases, at least one of the iodine-containing substance, the sulfur oxide species, the solvent and the carbonaceous material may be mixed with others only when they are used in a process for liquefaction of carbonaceous materials. The carbonaceous material can be any suitable carbonaceous material that needs to be liquefied or contains at least a portion to be liquefied, such as coal including bituminous coal, brown coal, hard coal, sub-bituminous coal, anthracite coal, peat and lignite, oil shale, petroleum, tar sands, oil shale, and man-made residual oils, tars and heavy hydrocarbon residues, and mixtures thereof. In some cases, the carbonaceous material may be in the form of particles having an average diameter of 1-5000pm, preferably 10-500pm, more preferably 50-250pm, most preferably 70-100Nm. In some cases, the moisture of carbonaceous material is less than 10%, preferably iess than 5%, more preferably less than 2%.
In certain embodiments of the present invention, if appropriate, two or more or all components of the catalyst combination may form a solution or a mixture such as suspension, slurry or powder, while other components, if any, may be in their original forms individually or form other mixtures and/or solutions. In some cases, each of mixtures or solutions or components in the catalyst combination may be kept individually during manufacture, transportation and/or storage, for example, they may be packaged in different containers individualiy or in different chambers of one or more containers. This may be advantageous under some situations to avoid, if any, for example, undesired interactions between components before they are used as a catalyst combination, or to facilitate the manufacture, transportation and/or storage of such catalyst combination. In some embodiments, all components may be in their original forms individually and kept individually during manufacture, transportation and/or storage. However, in any above case, all components of the catalyst combination are considered as a whole and are used together at the same time or in any suitable order in a process for liquefaction of carbonaceous materials. In some embodiments, the catalyst combination is a solution or a mixture, which comprises an iodine-containing substance and a sulfur oxide species. In some other cases, when two or more of the components in the combination are mixed together, they may have, if appropriate, a physical or chemical interaction between each other, providing that the interaction does not significantly interfere the liquefaction of carbonaceous materials.
In the present invention, the ratio of components in the catalyst combination may be determined according to actual conditions and requirements. In some embodiments, the weight ratio of iodine-containing substance : sulfur oxide species is 0.2-10 : 0.5-20, preferably 1-5 : 5-15. In the case that the catalyst combination comprises a solvent and/or a carbonaceous material, the weight ratio of iodine-containing substance : sulfur oxide species : solvent : carbonaceous material is 0.2-10 : 0.5-20 : 0-1000 : 0-100, preferably 1-5 : 5-15 : 0-200 0-50, more preferably 1-2 : 6-10 : 0-150 : 0-50.
In some embodiments of the present invention, the iodine-containing substance and/or sulfur oxide species used in the process for liquefaction of carbonaceous materials may be at least partially or totally provided by a catalyst combination as described hereinabove. For example, in some embodiments, the process may use only the catalyst combination in accordance with the present invention to provide the needed iodine-containing substance and sulfur oxide species, while in other embodiments, the process may use the catalyst combination described herein to provide a portion of iodine-containing substance and a portion of sulfur oxide species. Similarly, the carbonaceous materials and the solvent used in the process may be partially or totally provided by the catalyst combination in accordance with the present invention as well. In some embodiments, besides those contained in the catalyst combination as described herein, the process may further use additional same or different iodine-containing substance, sulfur oxide species, solvent and/or carbonaceous material as described hereinabove.
In some embodiments of the present invention, the carbonaceous materials to be liquefied in the process of the present invention may be any suitable carbonaceous materials that needs to be liquefied or contains at least a portion to be liquefied, and examples of the carbonaceous materials may include coal such as bituminous coal, brown coal, hard coal, sub-bituminous coal, anthracite coal, peat and lignite, oil shale, petroleum, tar sands, oil shale, man-made residual oils, tars, heavy hydrocarbon residues, and mixtures thereof.
In some embodiments of the present invention, the solvent used in the process may serve as a liquid vehicle and/or a hydrogen-donor. Examples of such solvent may comprise hydroaromatic solvents, such as tetralin, tetrahydroquinoline, piperidine, indoline, perhydropyrene, pyrolidine, as well as hydrogenated anthracene oil, hydrogenated coal liquids, catalytic cracking residual oil, heavy hydrocarbon residues, and mixtures thereof.
In some embodiments of the process, the hydrogen-donor may be a hydrogen-containing compound or a mixture comprising such compound, and the examples of hydrogen-donor may include natural gas, coal-bed gas, methane, ethane, coal oven gas, hydrogen gas, or a mixture thereof. In some cases, the gas may further comprise hydrogen gas and/or an inert gas such as noble gas and nitrogen gas. In some embodiments, natural gas, coal-bed gas and/or coal oven gas is used directly, or is used to replace 50-100% by volume of the methane in a mix consisting of methane and hydrogen in a ratio of 99:1 - 1:99.
In another embodiment, natural gas or methane is solely used as the hydrogen-donor.
In the process of the present invention, the components of iodine-containing substance, sulfur oxide species, solvent and carbonaceous material may be added in a reactor simultaneously or in sequence by any order.
In the present invention, the ratio of components used in the process may be determined according to actual conditions and requirements. In some embodiments, the weight ratio of iodine-containing substance : sulfur oxide species : solvent : carbonaceous material in the process is 0.2-10 : 0.5-20 50-1000 : 10-100, preferably 1-5 : 5-15 : 70-200 : 100, more preferably 1-2 6-10 : 100-150 : 100.
In some embodiments of the process, the hydrogen-donor is provided in a gaseous form with a cold pressure of 0.1 -10MPa, preferably 2-9MPa, more preferably 3-5MPa.
In some embodiments of the process, the carbonaceous material contacts with the hydrogen-donor in the solvent under a temperature between 250 C and 750 C, preferably between 280 C and 500 C, more preferably between 280 C and 420 C, and a pressure between 0.2MPa and 20MPa, preferably between 5MPa and 15MPa, more preferably between 7MPa and 12MPa for a time period of 0.5-24 hours, preferably 0.5-12 hours, more preferably 0.5-4 hours.
In some embodiments of the present invention, without limitation of any theory, it is believed that the iodine-containing substance may serve as a primary catalyst, the sulfur oxide species may serve as a co-catalyst, and the solvent may serve as both a vehicle as well as a reactant such as a hydrogen-donor, and the presence of the hydrogen-donor solvent together with the hydrogen-donor gas such as methane may increase the yield of desired liquid and gaseous hydrocarbons during the liquefaction of carbonaceous materials.
In some embodiments of the present invention, the iodine-containing substance, sulfur oxide species, solvent and/or carbonaceous material may be used in the form of a solid-liquid or liquid-liquid reaction mixture and fed into a reaction vessel and pressurized to an elevated pressure. In some cases, the reaction mixture may be preheated up to 100 C, preferably to 80-90 C, before introducing it into a reaction vessel. When the contents of the reaction vessel are heated to the reaction temperature, the reaction occurs between the carbonaceous, solvent and hydrogen-donor gas such as methane. This results in the formation of new and useful liquid products and gaseous products.
In some embodiments of the present invention, the process may further comprise: (3) separating a liquefaction product from a reaction mixture after the liquefaction.
In some embodiments of the present invention, the process may further comprise: (4) directly recycling the residue after the separation, or separating the iodine-containing substance, sulfur oxide species, solvent and/or carbonaceous material from the residue and optionally recycling at least one of them.
In some embodiments of the present invention, the liquefaction product can be any desired liquid and gaseous products which could be separated from a reaction mixture after liquefaction, in which the examples of suitable separation means may comprise centrifugation, distillation, vaporization, filtration, extraction and so on. In some cases, at least a part of the residue after the separation may be directly recycled without any further separation. In some other cases, the residue may be further separated to obtain the iodine-containing substance, sulfur oxide species, solvent and/or carbonaceous material, and at least one of them may be recycled to replace at least partial or total iodine-containing substance, sulfur oxide species, solvent and/or carbonaceous material used in the process for liquefaction of carbonaceous materials. In some other cases, the liquid and gaseous products obtained by the separation may also be further processed to obtain a solvent and/or hydrogen-donor gas which can be used as solvent and/or hydrogen-donor gas in the next turn of process for liquefaction of carbonaceous materials.
EXAMPLES
Although the present invention is described in terms of specific materials and process steps, it will be clear to one skilled in the art that various changes and modifications may be made in accordance with the invention described in the accompanying claims.
The following examples are presented merely by way of illustration and are not intended to limit the present invention beyond that defined in the accompanying claims.
In the following examples, Inner Mongolia lignite, Shanxi bituminous coal are ground to a diameter of less than 0.1 mm, classified as <160mesh (about 100 micrometers) and <200mesh (about 75 micrometers) respectively, dried under vacuum at 100 C for 24hrs, and used as feedstock. The results of elemental analyses of these raw coals are summarized in Table 1.
Table 1. Elemental analyses of raw coals Inner Mongolia Shanxi bituminous lignite coal coal Elemental analysis, %, dmmf C 61.1 77.86 H 2.79 4.32 S(total) 1.60 1.31 O(by difference) 8.06 8.16 H/C 0.55 0.67 Proximate analysis, %
Moisture, as received 5.94 2.47 Fixed carbon, dry 53.72 64.76 Volatile matter, dry 20.50 27.67 Calorific value, KJ/kg 23590 31480 In the following examples, the solid and liquid reaction products are analyzed by solvent fractionation using a series of extraction solvents, and the amount of gaseous products are determined by weighing the gases in the reactor before and after the gaseous products are released from the reactor.
The liquid products are fractionated by using a series of solvents into a hexane-soluble fraction (HXs); a tetrahydrofuran(THF)-soluble, hexane-insoluble fraction; and a THF-insoluble fraction which is also defined as an insoluble organic matter (IOM) that is moisture and ash free (maf). The amount of each of the fractions, except for the HXs, is determined by weighing the fraction after the solvent is evaporated off. The HXs is determined by a different way so that all losses, including those due to the escape of volatiles, are counted in this fraction.
Thus, the conversion refers to a weight conversion of carbonaceous material, and is calculated by using the following equation.
%convers;on = 1-910M x 100 g maf Wherein %conversion represents the weight convention of the carbonaceous material; gioM represents the weight of THF-insoluble organic matter after the reaction, which is calculated by the following equation: g,oM = (the weight of the THF-insoluble fraction after the reaction) - (the weight of moisture and ash in the original carbon carbonaceous material); and gmaf represents the weight of the moisture and ash free carbonaceous material, which is calculated by the equation:
gn,af = (the weight of the original carbonaceous material) - (the weight of moisture and ash in the original carbon carbonaceous material).
The HS yield refers to a weight yield of the n-hexane-soluble liquid and gaseous products, and is calculated by using the following equation.
HS yield (wt%) = [(the weight of the original carbon carbonaceous material) +
(the weight loss of the hydrogen-donor) - (the weight of the n-hexane-insoluble fraction)]/(the weight of the original carbon carbonaceous material) Example 1 About 150 grams of tetralin as solvent were added to 75 grams of particulate Inner Mongolia lignite coal having a particle size of less than 100 micrometers to form a suspension A. About 0.35 gram of potassium iodide and 10 grams of 20%
oleum were mixed with the suspension A, which was then loaded in an autoclave with a capacity of 1000-m1 for direct liquefaction.
The air of the autoclave was firstly replaced by nitrogen for three times, and then gaseous methane (cold pressure of 5.OMPa) was introduced into the autoclave. The autoclave was then sealed and heated to 300 C for 1 h under an autogenous pressure (10MPa) with vigorous stirring (400rpm).
After the end of reaction, the gaseous, liquid and solid products of coal liquefaction were recovered from the autoclave by washing out with tetrahydrofuran (THF). After THF was removed by evaporation at 80 C under vacuum for 12 hours, the resultant residue was extracted with n-hexane by Soxhlet Extraction for 24 hours and dried at a temperature of 80 C under vacuum for 12 hours to obtain an n-hexane insoluble fraction, then the n-hexane insoluble fraction was further extracted with THF by Soxhlet extraction for 24 hours and dried at a temperature of 80 C under vacuum for 24 hours to obtain a THF-insoluble fraction. The conversion and HS yield were calculated in accordance with the above equations and the results were shown in Table 2.
Example 2 About 75 grams of hydrogenated anthracene oil as solvent were added to 75 grams of particulate Inner Mongolia lignite coal having a particle size of less than 75 micrometers to form a suspension B. About 3.75 grams of sodium iodide and 15 grams of 40% oleum were mixed with suspension B, and then the mixture was loaded in an autoclave with a capacity of 1000-m1 for direct liquefaction.
The air of the autoclave was firstly replaced by nitrogen gas for three times, and then gaseous methane (cold pressure of 2.OMPa) was introduced into the autoclave. The autoclave was then sealed and heated to 380 C for 4 h under autogenous pressure (about 7MPa) with vigorous stirring (400rpm).
After the end of reaction, the gaseous, liquid and solid products of coal liquefaction were treated as in Example 1. The results of Example 2 are shown in Table 2.
Example 3 About 300 grams of catalytic cracking residual oil as solvent were added to 75 grams of particulate Shanxi bituminous coal having a particle size of less than 100 micrometers to form a suspension C. About 0.15 grams of boron triiodide and 3.75 grams of 60% oleum were mixed with suspension C, and then the mixture are subjected to direct liquefaction in an autoclave with capacity of 1000-m1.
The air of the autoclave was firstly replaced by nitrogen gas for three times, and then gaseous methane (cold pressure of 4.OMPa) was introduced to the autoclave. The autoclave was then sealed and heated to 420 C for 3 h under autogenous pressure (9 MPa) with vigorous stirring (400rpm).
After the reaction, the gaseous, liquid and solid products of coal liquefaction were treated as in Example 1. The results of Example 3 are shown in Table 2.
Example 4 About 500 grams of tetralin as solvent were added to 75 grams of particulate Shanxi bituminous coal having a particle size of less than 75 micrometers to form a suspension D. About 7.5 grams of potassium iodate, and 11.25 grams of 50%
oleum were mixed with suspension D, and then the mixture was subjected to direct liquefaction in an autoclave of 1000-m1 capacity.
The air of the autoclave was firstly replaced by nitrogen gas for three times, and then gaseous natural gas (cold pressure of 10 MPa) was introduced to the autoclave. The autoclave was then sealed and heated to 280 C for 2 h under autogenous pressure (12 MPa) with vigorous stirring (400rpm).
After the reaction, the gaseous, liquid and solid products of coal liquefaction were treated as in Example 1. The results of Example 4 are shown in Table 2.
Example 5 About 250 grams of a heavy hydrocarbon residue as solvent were added to 75 grams of particulate Inner Mongolia lignite coal having a particle size less than 100 micrometers to form a suspension E, in which the heavy hydrocarbon residue was distilled from the liquid product of Example 1 and had a boiling point range of about 350-400 C. About 0.75 grams of sodium iodate and 0.75 grams of solid sulfur trioxide were mixed with suspension E, and then the mixture was subjected to direct liquefaction in an autoclave of 1000-m1 capacity.
The air of the autoclave was firstly replaced by nitrogen gas for three times, and then gaseous methane (cold pressure of 3.0 MPa) was introduced to the autoclave. The autoclave was then heated to 330 C for 0.5 h under autogenous pressure (7.5 MPa) with vigorous stirring (400rpm).
After the reaction, the gaseous, liquid and solid products of coal liquefaction were treated as in Example 1. The results of Example 5 are shown in table 2.
Example 6 The procedure of Example 1 was followed, except 0.1 gram of iodine and 0.25 gram of diiodine pentoxide instead of 0.35 gram of potassium iodide were used in Example 6.
After the reaction, the gaseous, liquid and solid products of coal liquefaction were treated as in Example 1. The results of Example 6 are shown in Table 2.
Table 2. Results of Examples 1-6 Run Coal Particle Conversion HS yield size (pm) (wt%) (wt%) Example 1 Lignite <100 47.39 37.03 Example 2 Lignite <75 54.6 37.14 Example 3 Bituminous <100 55.95 37.19 Example 4 Bituminous <75 56.33 37.74 Example 5 Lignite <100 57.5 45.53 Example 6 lignite <100 53.3 40.26 Comparative Examples 1~5 The comparative examples 1-5 were conducted respectively under the same conditions of Examples 1-5, except that no catalyst and co-catalyst was used in the comparative examples 1-5. The results of the comparative examples 1-5 are shown in Table 3.
Table 3. Results of Comparative Examples 1-5 Run Coal Particle Conversion HS yield size (pm) (wt%) (wt%) Comparative Example 1 Lignite <100 32.49 25.13 Comparative Example 2 Lignite <75 35.5 30.05 Comparative Example 3 Bituminous <100 37.87 29.2 Comparative Example 4 Bituminous <75 33.33 28.95 Comparative Example 5 Lignite <100 34.85 32.23 It can be seen from the above examples and comparative examples that the catalyst combination in accordance with the present invention exhibited significant effects in direct liquefaction of carbonaceous materials. For example, when the catalyst combination of the present invention was used, the conversion and HS
yield increased significantly. It was also indicated that the direct liquefaction of carbonaceous materials by using the catalyst of the present invention could be implemented by using only methane as hydrogen-donor, rather than by using a hydrogen product such as hydrogen gas or a hydrogen-containing gas.
By reading the present invention, those skilled in the art would understand that the present invention is not intended to be limited by what is disclosed in the examples, and any modifications and variants without departing from the general concept of the present invention fall within the scope of the present invention.
Claims (21)
1. A catalyst combination for direct liquefaction of carbonaceous materials, comprising:
a) an iodine-containing substance, and b) a sulfur oxide species.
a) an iodine-containing substance, and b) a sulfur oxide species.
2. The catalyst combination according to claim 1, wherein the iodine-containing substance is selected from a group comprising iodine element, iodine oxide, iodic acid anhydride, ammonium iodide, alkaline metal iodides, alkaline earth metal iodides, ammonium iodate, alkaline metal iodates, alkaline earth metal iodates, boron iodide, and mixtures thereof, wherein the alkaline metal is lithium, sodium, potassium, rubidium, or cesium, and the alkaline earth metal is beryllium, magnesium, calcium, strontium, or barium.
3. The catalyst combination according to claim 1 or 2, wherein the sulfur oxide species is selected from a group comprising sulfur trioxide, sulfur dioxide, oleum, concentrated sulfuric acid, and mixtures thereof.
4. The catalyst combination according to any one of claims 1 to 3, wherein the catalyst combination further comprises a solvent.
5. The catalyst combination according to claim 4, wherein the solvent is a hydroaromatic solvent selected from a group comprising tetralin, tetrahydroquinoline, piperidine, indoline, perhydropyrene, pyrolidine, hydrogenated anthracene oil, hydrogenated coal liquids, catalytic cracking residual oil, and mixtures thereof.
6. The catalyst combination according to any one of claims 1 to 5, wherein the catalyst combination further comprises a carbonaceous material.
7. The catalyst combination according to claim 6, wherein the carbonaceous material is selected from a group comprising bituminous coal, brown coal, hard coal, sub-bituminous coal, anthracite coal, peat and lignite, oil shale, petroleum, tar sands, oil shale, man-made residual oils, tars and heavy hydrocarbon residues, and mixtures thereof.
8. The catalyst combination according to any one of claims 1 to 7, wherein the catalyst combination has a weight ratio of iodine-containing substance :
sulfur oxide species of 0.2~10 : 1~20.
sulfur oxide species of 0.2~10 : 1~20.
9. The catalyst combination according to any one of claims 6 to 7, wherein the catalyst combination has a weight ratio of iodine-containing substance :
sulfur oxide species : solvent : carbonaceous material of 0.2~10 : 0.5~20 : 0~1000 0~100.
sulfur oxide species : solvent : carbonaceous material of 0.2~10 : 0.5~20 : 0~1000 0~100.
10.A process for direct liquefaction of a carbonaceous material, comprising:
(1) providing a catalyst combination comprising a) an iodine-containing substance, and b) a sulfur oxide species;
(2) contacting a carbonaceous material with a hydrogen-donor in the presence of the catalyst combination optionally in a solvent under a temperature between 250°C and 750°C and a pressure between 0.2MPa and 20MPa.
(1) providing a catalyst combination comprising a) an iodine-containing substance, and b) a sulfur oxide species;
(2) contacting a carbonaceous material with a hydrogen-donor in the presence of the catalyst combination optionally in a solvent under a temperature between 250°C and 750°C and a pressure between 0.2MPa and 20MPa.
11.The process according to claim 10, wherein the catalyst combination is a catalyst combination according to any one of claims 1 to 9.
12.The process according to any one of claims 10 to 11, wherein the solvent is a hydroaromatic solvent selected from a group comprising tetralin, tetrahydroquinoline, piperidine, indoline, perhydropyrene, pyrolidine, hydrogenated anthracene oil, hydrogenated coal liquids, catalytic cracking residual oil, and mixtures thereof.
13.The process according to any one of claims 10 to 12, wherein the carbonaceous material is selected from a group comprising bituminous coal, brown coal, hard coal, sub-bituminous coal, anthracite coal, peat and lignite, oil shale, petroleum, tar sands, oil shale, man-made residual oils, tars and heavy hydrocarbon residues, and mixtures thereof.
14.The process according to any one of claims 10 to 13, wherein the hydrogen-donor is selected from a group comprising natural gas, coal-bed gas, methane, ethane, coal oven gas, hydrogen, and mixtures thereof.
15.The process according to any one of claims 10 to 14, wherein the weight ratio of iodine-containing substance : sulfur oxide species : solvent : carbonaceous material is 0.2~10 : 0.5~20 : 50~1000 : 10~100.
16.The process according to any one of claims 10 to 15, wherein the hydrogen-donor is provided in a gaseous form with a cold pressure of 0.1~10MPa.
17.The process according to any one of claims 10 to 16, wherein the carbonaceous material contacts with the hydrogen-donor under a temperature between 280°C and 420°C and a pressure between 7MPa and 12MPa for a time period of 0.5~24 hours.
18.The process according to any one of claims 10 to 17, wherein the process further comprises:
(3) separating a liquefaction product from a reaction mixture after the liquefaction.
(3) separating a liquefaction product from a reaction mixture after the liquefaction.
19.The process according to claim 18, wherein the process further comprises:
(4)directly recycling the residue after the separation, or separating the iodine-containing substance, sulfur oxide species, solvent and/or carbonaceous material from the residue and optionally recycling at least one of them.
(4)directly recycling the residue after the separation, or separating the iodine-containing substance, sulfur oxide species, solvent and/or carbonaceous material from the residue and optionally recycling at least one of them.
20.Use of a catalyst combination according to any one of claims 1 to 9 for direct liquefaction of a carbonaceous material.
21.The use according to claim 20, wherein the carbonaceous material is selected from a group comprising bituminous coal, brown coal, hard coal, sub-bituminous coal, anthracite coal, peat and lignite, oil shale, petroleum, tar sands, oil shale, man-made residual oils, tars and heavy hydrocarbon residues, and mixtures thereof.
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| CN200710201127.XA CN101348726B (en) | 2007-07-19 | 2007-07-19 | Coal direct liquefaction method |
| CN200710201127.X | 2007-07-19 |
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| CN102212388B (en) * | 2010-04-08 | 2014-06-25 | 肇庆市顺鑫煤化工科技有限公司 | Separation method and devices of thermal dissolution and catalysis liquefied product of lignite |
| CN103555357B (en) * | 2013-11-04 | 2015-08-19 | 华东理工大学 | The processing method of a kind of coal gentleness liquefaction |
| CN111188594B (en) * | 2020-02-22 | 2021-11-19 | 太原理工大学 | Old goaf coal slime water gas-liquid fluidized mining device and method |
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| GB1310283A (en) * | 1970-06-12 | 1973-03-14 | Shell Int Research | Process for hydrogenative cracking of carbonaceous material |
| US3790469A (en) * | 1973-03-16 | 1974-02-05 | Shell Oil Co | Hydrocracking coal in molten zinc iodide |
| US4824558A (en) * | 1987-09-04 | 1989-04-25 | Exxon Research And Engineering Company | Coal liquefaction process with metal/iodine cocatalyst |
| CN1072703C (en) * | 1998-07-20 | 2001-10-10 | 中国科学院山西煤炭化学研究所 | Method for direct liquefaction of coal using FeSOX as presoma of catalyst therefor |
| US20060029893A1 (en) * | 2004-08-09 | 2006-02-09 | Kuai-Teng Hsu | Process and system of power generation |
| CN100457261C (en) * | 2005-04-27 | 2009-02-04 | 中国石油化工股份有限公司 | Iron-based coal liquefied catalyst and production thereof |
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