CN112007653A - Direct coal liquefaction catalyst, preparation method and application thereof, and direct coal liquefaction method - Google Patents
Direct coal liquefaction catalyst, preparation method and application thereof, and direct coal liquefaction method Download PDFInfo
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- CN112007653A CN112007653A CN202010845038.4A CN202010845038A CN112007653A CN 112007653 A CN112007653 A CN 112007653A CN 202010845038 A CN202010845038 A CN 202010845038A CN 112007653 A CN112007653 A CN 112007653A
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- Prior art keywords
- catalyst
- coal liquefaction
- direct
- molybdenum
- coal
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- 239000003245 coal Substances 0.000 title claims abstract description 132
- 239000003054 catalyst Substances 0.000 title claims abstract description 107
- 238000000034 method Methods 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 103
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 52
- 238000006243 chemical reaction Methods 0.000 claims abstract description 40
- 239000011701 zinc Substances 0.000 claims abstract description 30
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 23
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 23
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 22
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000002817 coal dust Substances 0.000 claims abstract description 8
- 229910052742 iron Inorganic materials 0.000 claims description 41
- 229910052750 molybdenum Inorganic materials 0.000 claims description 30
- 239000011733 molybdenum Substances 0.000 claims description 29
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 28
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 28
- 229910052751 metal Inorganic materials 0.000 claims description 25
- 239000002184 metal Substances 0.000 claims description 25
- 238000001556 precipitation Methods 0.000 claims description 20
- 150000002751 molybdenum Chemical class 0.000 claims description 15
- 239000012266 salt solution Substances 0.000 claims description 15
- 239000002245 particle Substances 0.000 claims description 13
- 150000003754 zirconium Chemical class 0.000 claims description 13
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 12
- 150000002505 iron Chemical class 0.000 claims description 12
- 150000003751 zinc Chemical class 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 11
- 238000000227 grinding Methods 0.000 claims description 11
- 150000003839 salts Chemical class 0.000 claims description 10
- 239000002002 slurry Substances 0.000 claims description 10
- 239000012752 auxiliary agent Substances 0.000 claims description 9
- 239000012018 catalyst precursor Substances 0.000 claims description 9
- 239000012065 filter cake Substances 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- -1 zirconium ions Chemical class 0.000 claims description 4
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 2
- 239000011609 ammonium molybdate Substances 0.000 claims description 2
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 2
- 229940010552 ammonium molybdate Drugs 0.000 claims description 2
- 150000002823 nitrates Chemical class 0.000 claims description 2
- 150000003467 sulfuric acid derivatives Chemical group 0.000 claims description 2
- 230000014759 maintenance of location Effects 0.000 claims 1
- 239000000758 substrate Substances 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 19
- 230000000694 effects Effects 0.000 abstract description 10
- 239000000126 substance Substances 0.000 abstract description 2
- 239000003921 oil Substances 0.000 description 15
- 239000006185 dispersion Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 230000002195 synergetic effect Effects 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 239000004480 active ingredient Substances 0.000 description 5
- 239000002131 composite material Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 239000003250 coal slurry Substances 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- KWUUWVQMAVOYKS-UHFFFAOYSA-N iron molybdenum Chemical compound [Fe].[Fe][Mo][Mo] KWUUWVQMAVOYKS-UHFFFAOYSA-N 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000011282 treatment Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 2
- 239000010426 asphalt Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N ferric oxide Chemical compound O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 239000011790 ferrous sulphate Substances 0.000 description 2
- 235000003891 ferrous sulphate Nutrition 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical group [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 description 2
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 2
- ZXAUZSQITFJWPS-UHFFFAOYSA-J zirconium(4+);disulfate Chemical group [Zr+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZXAUZSQITFJWPS-UHFFFAOYSA-J 0.000 description 2
- 229910006299 γ-FeOOH Inorganic materials 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- 229910017076 Fe Zr Inorganic materials 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- 238000000944 Soxhlet extraction Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 229910008159 Zr(SO4)2 Inorganic materials 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000004931 aggregating effect Effects 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000002153 concerted effect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000009837 dry grinding Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 150000002506 iron compounds Chemical class 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000010742 number 1 fuel oil Substances 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 description 1
- 229910052683 pyrite Inorganic materials 0.000 description 1
- 239000011028 pyrite Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- 239000011686 zinc sulphate Substances 0.000 description 1
- GBNDTYKAOXLLID-UHFFFAOYSA-N zirconium(4+) ion Chemical compound [Zr+4] GBNDTYKAOXLLID-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8873—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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0201—Oxygen-containing compounds
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
-
- 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
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/394—Metal dispersion value, e.g. percentage or fraction
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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
- C10G1/06—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by destructive hydrogenation
- C10G1/065—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by destructive hydrogenation in the presence of a solvent
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
- C10G1/08—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal with moving catalysts
- C10G1/083—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal with moving catalysts in the presence of a solvent
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Materials Engineering (AREA)
- Nanotechnology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Composite Materials (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention relates to the technical field of coal chemical industry, in particular to a direct coal liquefaction catalyst, a preparation method and application thereof, and a direct coal liquefaction method. The direct coal liquefaction catalyst comprises a carrier and an active component, wherein the active component comprises a main active component and an auxiliary component, and the carrier is coal dust; wherein the main active component comprises iron element and molybdenum element, and the auxiliary component comprises zinc element and optional zirconium element. The direct coal liquefaction catalyst provided by the invention has high catalytic activity and high dispersibility, so that the direct coal liquefaction effect is improved. Meanwhile, the direct coal liquefaction catalyst provided by the invention is used for direct coal liquefaction, and can effectively improve the conversion rate and the oil yield of coal.
Description
Technical Field
The invention relates to the technical field of coal chemical industry, in particular to a direct coal liquefaction catalyst, a preparation method and application thereof, and a direct coal liquefaction method.
Background
The direct coal liquefaction is that coal is firstly ground into coal powder and then mixed with solvent (petroleum fraction) to prepare coal oil slurry, then the coal slurry is directly subjected to hydrocracking reaction with hydrogen under the action of high temperature, high pressure and catalyst, so that the coal is directly converted into liquid oil product, and the catalyst plays an important role in the coal slurry, can effectively promote the pyrolysis and hydrogenation of the coal, and can improve the yield of the produced oil and the quality of the oil product.
In the direct coal liquefaction process, the catalyst enters the reactor along with the common feeding of coal slurry to participate in the reaction, and then is discharged out of the system together with the product, and the catalyst is generally not recycled, so that the catalyst has high requirements on the cost of the catalyst. The iron catalyst has good activity and low price, and most of the processes use the iron catalyst; the catalysts with higher activity such as cobalt, molybdenum, nickel and the like are gradually abandoned or only used as iron catalyst auxiliaries due to higher price. Partial grindingThe iron ore with large yield and low price is used as a catalyst, such as: CN1014418A and CN1298920A disclose methods of using natural high-grade iron ore as a direct coal liquefaction catalyst, in which iron ore is pulverized into micron-sized particles by multi-stage pulverization and added into a direct coal liquefaction reaction, wherein CN1014418A further needs pre-reduction treatment of iron ore, and these treatments inevitably increase energy consumption and cost. More researchers tend to synthesize highly active iron catalysts by artificial methods, such as: CN1231326A discloses a nano amorphous Fe (OH)3Or Fe (OH)2As a direct coal liquefaction catalyst, the particle size of iron-based primary particles is about 30-80nm, and the catalytic activity is higher than that of natural pyrite. CN1579623A discloses a high-dispersion gamma-FeOOH iron-based coal direct liquefaction catalyst and a preparation method thereof, wherein gamma-FeOOH is loaded on coal dust to enable active components to be fully contacted with raw material coal dust, so that the coal direct liquefaction efficiency is improved. CN101947472A discloses a method for using an oleic acid coated iron trioxide nanocrystal as a direct coal liquefaction catalyst, and the catalyst has the advantages of high dispersibility, good oil solubility, no toxicity, no harm, high catalytic activity, good selectivity, high oil yield and high conversion rate.
The catalysts are all prepared by reducing the particle size of iron-containing compounds by a proper method to improve the dispersibility, so as to improve the activity of the iron-based catalyst and reduce the using amount. The catalysts are usually limited to active species derived from iron element, the activity is difficult to be effectively improved, the usage amount is still high, and the conversion efficiency of coal and the yield of coal liquefaction oil are difficult to meet ideal requirements; in addition, the synthesis method and treatment method of the catalyst are complicated, and the cost for producing the catalyst is also greatly increased.
Disclosure of Invention
The invention aims to solve the problems of low yield of coal direct liquefaction oil, low coal conversion rate and the like of the prior art due to weak intrinsic activity and poor dispersibility of the coal direct liquefaction catalyst, and provides a coal direct liquefaction catalyst, a preparation method and application thereof, and a method for direct coal liquefaction. The direct coal liquefaction catalyst has high catalytic activity and high dispersibility, so that the direct coal liquefaction effect is improved.
In order to achieve the above object, a first aspect of the present invention provides a direct coal liquefaction catalyst, the catalyst comprising a carrier and an active component, the active component comprising a main active component and an auxiliary component, the carrier being pulverized coal;
wherein the main active component comprises iron element and molybdenum element, and the auxiliary component comprises zinc element and optional zirconium element.
Preferably, in the active component, the molar ratio of the main active component to the auxiliary component is 1-50: 1.
Preferably, in the main active component, the molar ratio of the iron element to the molybdenum element is 15-250: 1.
Preferably, in the auxiliary agent component, the molar ratio of the zinc element to the zirconium element is 1-10: 0-1.
The second aspect of the present invention provides a method for preparing a catalyst for direct coal liquefaction, comprising the steps of:
(1) mixing iron salt, zinc salt, optional zirconium salt and deionized water to obtain a metal salt solution, and dissolving molybdenum salt in ammonia water to obtain an ammonia solution containing molybdenum;
(2) carrying out precipitation reaction on the molybdenum-containing ammonia solution and a metal salt solution, and adding ammonia water to adjust the pH value of the mixed solution to 5.5-9 to obtain precipitation slurry;
(3) mixing the precipitation slurry with coal powder to obtain a catalyst precursor;
(4) and sequentially filtering, drying and grinding the catalyst precursor to obtain the direct coal liquefaction catalyst.
The third aspect of the invention provides an application of the direct coal liquefaction catalyst provided by the first aspect and/or the direct coal liquefaction catalyst prepared by the method provided by the second aspect in direct coal liquefaction.
The fourth aspect of the invention provides a method for directly liquefying coal by using the direct coal liquefaction catalyst provided by the first aspect and/or the direct coal liquefaction catalyst prepared by the method provided by the second aspect;
wherein the conditions for direct coal liquefaction comprise: the reaction temperature is 400-500 ℃, preferably 440-460 ℃; the reaction pressure is 5-30MPa, preferably 15-25 MPa; the residence time is from 1 to 10 hours, preferably from 1 to 5 hours.
According to the technical scheme, the auxiliary components containing the zinc element and the optional zirconium element are introduced, particularly the zinc element and the zirconium element are introduced simultaneously, so that the high dispersion and electronic structure of the main active components (the iron element and the molybdenum element) in the coal direct liquefaction catalyst are improved, the synergistic catalytic action of the iron element and the molybdenum element and the co-catalytic action of the auxiliary components on the main active components are exerted simultaneously, and the catalytic activity of the coal direct liquefaction catalyst is improved.
Compared with the prior art, the invention has the following advantages:
(1) the invention limits the active component in the catalyst to contain a main active component and an auxiliary component, particularly introduces the auxiliary component containing zinc element and zirconium element, and promotes the synergistic catalytic action between the iron and molybdenum double active components through the cocatalyst performance of the auxiliary component to the main active component;
specifically, firstly, an electron assistant Zn and a main active component Fe are coprecipitated to form Fe-Zn composite hydrated oxide, and Zn provides electrons for a d orbit of Fe in the coal liquefaction process, so that more sulfur vacancies are generated in an active phase, the hydrogen activation capability is improved, and the asphalt is promoted to be converted into oil; secondly, the main active component Mo is dispersed on the surface of the iron hydrated oxide, so that hydrogen overflow is possible, the electron-donating property of the electronic assistant Zn can further promote the hydrogen overflow, and the concerted catalysis between iron and molybdenum is enhanced; finally, the existence of the structure auxiliary agent Zr inhibits the nano-scale iron-molybdenum active species (namely, the compound formed by combining iron, molybdenum and sulfur) generated in situ in coal liquefaction from aggregating and sintering during the coal liquefaction reaction, so that the nano-scale iron-molybdenum active species can continuously and stably play a catalytic role;
(2) according to the direct coal liquefaction catalyst provided by the invention, the auxiliary agent component containing zinc element and zirconium element is particularly introduced, so that the multistage dispersion of the main active components of iron and molybdenum is realized, and the catalytic performance of the main active components is fully exerted;
specifically, firstly, a structural assistant Zr is introduced to ensure that Fe and Zr form Fe-Zr composite hydrated oxide when being coprecipitated, so that Fe and Mo are promoted to form nanoscale iron hydrated oxide and nanoscale iron-molybdenum composite hydrated oxide, the nanoscale high dispersion of active ingredients is realized, and the catalytic capability of active metal of unit weight is improved; secondly, depositing and enriching an active component Mo on the surface of the iron hydrous oxide, so that the Mo is exposed on the surface of the catalyst and reaches molecular-level dispersion, the molar ratio of the iron element to the molybdenum element is further limited, and the catalytic hydrogenation capacity of the catalyst is improved;
(3) the invention takes the liquefied raw material coal powder as a carrier, so that the active components of iron and molybdenum are dispersed and adsorbed on the inner surface and the outer surface of the coal powder particles, micron-scale dispersion is realized, the active components and partial reactants are in zero-distance contact, and the function of catalyzing coal liquefaction can be more effectively exerted.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
In order to achieve the above object, a first aspect of the present invention provides a direct coal liquefaction catalyst, the catalyst comprising a carrier and an active component, the active component comprising a main active component and an auxiliary component, the carrier being pulverized coal;
wherein the main active component comprises iron element and molybdenum element, and the auxiliary component comprises zinc element and optional zirconium element.
According to the invention, the molar ratio of the main active component to the auxiliary component in the active component is preferably 1-50:1, preferably 2-40:1, wherein the main active component is calculated by the total mole of the iron element and the molybdenum element, and the auxiliary component is calculated by the total mole of the zinc element and the zirconium element. When the content of the auxiliary agent component is too high, excessive Fe-O-Zn and Fe-O-Zr composite species can be formed, so that the difficulty of converting the formed iron compound into an active phase is increased, and the activity is reduced; when the content of the auxiliary component is too low, the structure-improving ability is weakened, and the dispersing effect on the main active component is reduced.
According to the present invention, it is preferable that the molar ratio of the iron element to the molybdenum element in the main active component is 15 to 250:1, preferably 30 to 200: 1. The preferable conditions are adopted, so that the molybdenum element in the catalyst can be fully dispersed on the surface of the iron element, and the synergistic catalytic action of the two active components of iron and molybdenum is better exerted. When the content of the molybdenum element is excessive, the molybdenum element is aggregated and difficult to form molecular-level dispersion, so that the utilization rate of the molybdenum element is reduced, the gain on the catalytic action is not large, and the cost of the catalyst is increased; when the content of the molybdenum element is too low, the function of the molybdenum element cannot be exerted, and particularly the capability of activating hydrogen by synergistic strengthening between the molybdenum element and iron is reduced.
Preferably, in the auxiliary agent component, the molar ratio of the zinc element to the zirconium element is 1-10:0-1, preferably 1-8: 1. The optimized conditions are adopted to improve the dispersity and catalytic activity of the direct coal liquefaction catalyst, so that the conversion rate and oil yield of direct coal liquefaction are improved.
In some embodiments of the present invention, it is preferred that the support is present in an amount of 20 to 80 wt%, preferably 30 to 70 wt%, based on the total weight of the catalyst. The preferred conditions are adopted to provide good dispersion of the carrier into the main active ingredient and the adjunct ingredients. When the carrier content exceeds a certain amount, the dispersibility does not change much, but the energy consumption of dry grinding is increased; when the content of the carrier coal dust is too low, the main active component and the auxiliary agent component in the catalyst can be aggregated, so that the activity of the catalyst is reduced.
In some embodiments of the present invention, it is preferred that the average particle size of the pulverized coal is 150 μm or less, preferably 80 μm or less.
According to the invention, the catalyst preferably has a particle size of 80 μm or less; wherein the particle size is measured by a laser particle sizer.
The second aspect of the invention is a preparation method of a direct coal liquefaction catalyst, which comprises the following steps:
(1) mixing iron salt, zinc salt, optional zirconium salt and deionized water to obtain a metal salt solution, and dissolving molybdenum salt in ammonia water to obtain an ammonia solution containing molybdenum;
(2) carrying out precipitation reaction on the molybdenum-containing ammonia solution and a metal salt solution, and adding ammonia water to adjust the pH value of the mixed solution to 5.5-9 to obtain precipitation slurry;
(3) mixing the precipitation slurry with coal powder to obtain a catalyst precursor;
(4) and sequentially filtering, drying and grinding the catalyst precursor to obtain the direct coal liquefaction catalyst.
In the present invention, the mixing manner in step (1) has a wide selection range, as long as the iron salt, the zinc salt, the optional zirconium salt and the deionized water are uniformly mixed. Preferably, the iron salt is mixed with deionized water, and then the zinc salt and the optional zirconium salt are sequentially added and mixed.
In some embodiments of the present invention, preferably, in the metal salt solution, the mass concentration of the metal salt is 1 to 15%, preferably 3 to 10%, wherein the metal salt is based on the total mass of the iron ion, the zinc ion and the zirconium ion; further preferably, the metal salt is selected from sulfates and/or nitrates of at least one of iron, zinc and zirconium.
In the present invention, the iron salt, the zinc salt, and the zirconium salt have a wide range of selection, as long as the iron salt, the zinc salt, and the zirconium salt respectively contain an iron element, a zinc element, and a zirconium element. Preferably, the iron, zinc and zirconium salts are each independently the corresponding sulfate and/or nitrate. For example, the iron salt is selected from at least one of ferrous sulfate, ferric sulfate, ferrous nitrate, and ferric nitrate; the zinc salt is selected from zinc sulfate and/or zinc nitrate; the zirconium salt is selected from zirconium sulfate and/or zirconium nitrate.
In the present invention, unless otherwise specified, the molybdenum salt is dissolved in the ammonia water, which means that the molybdenum salt is soluble in the ammonia water, or the molybdenum salt is dissolved in the ammonia water under the action of the assistant.
In the invention, the molybdenum salt is dissolved in the ammonia water, which is more favorable for improving the dispersibility of the main active components of iron and molybdenum, avoiding the aggregation of the iron and the molybdenum, and further reducing the catalytic performance of the catalyst.
In the present invention, there is a wide range of choices for the kind of the molybdenum salt, and preferably, the molybdenum salt is a soluble salt containing molybdenum, preferably ammonium molybdate.
Preferably, the mass concentration of ammonia in the ammonia water is 0.5-10%. Preferred conditions are adopted to facilitate the molybdenum salt to be dissolved in the ammonia water.
In some embodiments of the present invention, it is preferable that the molar ratio of the iron salt and the molybdenum salt to the zinc salt and the zirconium salt is 1 to 50:1, preferably 2 to 40:1, wherein the iron salt and the molybdenum salt are calculated by the mole of the iron element and the molybdenum element, and the zinc salt and the zirconium salt are calculated by the mole of the zinc element and the zirconium element.
Further preferably, the molar ratio of the iron salt to the molybdenum salt is 15-250:1, preferably 30-200:1, wherein the iron salt is calculated by the mole of the iron element and the molybdenum salt is calculated by the mole of the molybdenum element; the molar ratio of the zinc salt to the zirconium salt is 1-10:0-1, preferably 1-8:1, wherein the zinc salt is calculated by the mole of the zinc element and the zirconium salt is calculated by the mole of the zirconium element.
In the invention, the precipitation reaction refers to the reaction of an ammonia solution containing molybdenum and a metal salt solution to obtain a precipitate containing iron, molybdenum, zinc and zirconium. Preferably, the precipitation reaction comprises: adding the molybdenum-containing ammonia solution to the metal salt solution.
Further preferably, the conditions of the precipitation reaction include: the temperature is 10-40 ℃, preferably 15-25 ℃; the time is 0.1-5h, preferably 0.5-3 h. The preferred conditions are adopted to be more favorable for forming the hydrated oxide of the composite metal with low grain size.
In some embodiments of the present invention, preferably, in step (2), ammonia water is added to adjust the pH of the mixed solution to 5.5 to 9, preferably 6.5 to 8.5, wherein the mixed solution is an ammonia solution containing molybdenum and a metal salt solution. The preferable conditions are adopted, which is more beneficial to the coprecipitation of the molybdenum and the iron, thereby realizing the high dispersion of the molybdenum on the surface of the iron hydrated oxide, being beneficial to the exertion of the catalytic activity of the molybdenum and improving the synergistic catalytic action of the iron and the molybdenum.
According to a preferred embodiment of the invention, the ammonia solution containing molybdenum is slowly dropped into the metal salt solution, so that metal ions in the mixed solution are subjected to precipitation reaction, the reaction temperature is 10-40 ℃, the reaction time is 0.1-5h, and ammonia water is added to adjust the pH value of the mixed solution to 5.5-9.
In the invention, the mass content of the coal dust in the finally obtained catalyst is ensured to be 20-70 wt%, and preferably, in the step (3), the weight ratio of the precipitation slurry to the coal dust is 3-20: 1.
In the present invention, the filtration method in the step (4) may be selected from a wide range as long as the catalyst precursor is subjected to solid-liquid separation.
In the present invention, the drying has a wide range of options as long as the washed cake is dried. Preferably, the drying conditions include: the temperature is 40-120 ℃, and the preferred temperature is 80-120 ℃; the time is 5-36h, preferably 10-24 h.
In the present invention, the grinding means grinding the dried filter cake to a particle size of 80 μm or less, preferably, the grinding is performed in a ball mill or a high-speed grinder.
According to the present invention, preferably, the method further comprises: and washing the filtered filter cake, and then sequentially drying and grinding.
In the invention, the washing comprises washing the filtered filter cake with absolute ethyl alcohol, wherein the amount of the absolute ethyl alcohol depends on the quality of the filtered filter cake. Preferably, the mass ratio of the absolute ethyl alcohol to the filtered filter cake is 1-10: 1.
the third aspect of the invention provides an application of the direct coal liquefaction catalyst provided by the first aspect and/or the direct coal liquefaction catalyst prepared by the method provided by the second aspect in direct coal liquefaction.
The fourth aspect of the invention provides a method for directly liquefying coal by using the direct coal liquefaction catalyst provided by the first aspect and/or the direct coal liquefaction catalyst prepared by the method provided by the second aspect;
wherein the conditions for direct coal liquefaction comprise: the reaction temperature is 400-500 ℃, preferably 440-460 ℃; the reaction pressure is 5-30MPa, preferably 15-25 MPa; the residence time is from 1 to 10 hours, preferably from 1 to 5 hours.
Preferably, the weight ratio of the coal direct liquefaction catalyst to dry coal is 0.2-0.8: 100, wherein the coal direct liquefaction catalyst is based on the total weight of iron and molybdenum in the main active component.
The present invention is explained below with reference to examples.
The specific parameter ranges of examples 1 to 12 are shown in Table 1, and the performance parameters of the coal direct liquefaction catalysts obtained in examples 1 to 12 and comparative examples 1 to 3 are shown in Table 3.
Example 1
(1) FeSO (ferric oxide) is added4·7H2Fully stirring and dissolving O and deionized water to obtain ferrous sulfate solution, adding ZnSO4·7H2O and Zr (SO)4)2·4H2O, obtaining a metal salt solution; will be (NH)4)6Mo7O24·4H2Mixing O with ammonia water with the mass concentration of 2.5 wt% to obtain an ammonia solution containing Mo;
(2) slowly dropping an ammonia solution containing Mo into a metal salt solution for precipitation reaction, wherein the conditions of the precipitation reaction comprise: the temperature is 35 ℃, the time is 60min, and ammonia water with the mass concentration of 2.5 wt% is added to adjust the pH value of the mixed solution to 7.5, so as to obtain precipitation slurry;
(3) mixing the precipitation slurry with coal powder with the average particle size of less than or equal to 150 mu m to obtain a catalyst precursor;
(4) and (2) centrifugally filtering the catalyst precursor, washing a filtered filter cake and absolute ethyl alcohol, wherein the mass ratio of the filtered filter cake to the absolute ethyl alcohol is 1:1, drying the washed filter cake in a 80 ℃ nitrogen drying oven for 24 hours, and grinding the dried product to be below 80 mu m to obtain the coal direct liquefaction catalyst S1.
Example 2
According to the method of example 1, except that (NH) is changed4)6Mo7O24·4H2The quality of O, specific parameter changes are shown in Table 1, and the coal direct liquefaction catalyst S2 is obtained.
Example 3
According to the method of example 1, except that (NH) is changed4)6Mo7O24·4H2The quality of O, specific parameter changes are shown in Table 1, and the coal direct liquefaction catalyst S3 is obtained.
Example 4
Following the procedure of example 1, except that ZnSO was changed4·7H2O and Zr (SO)4)2·4H2The quality of O, specific parameter changes are shown in Table 1, and the coal direct liquefaction catalyst S4 is obtained.
Example 5
Following the procedure of example 1, except that ZnSO was changed4·7H2O and Zr (SO)4)2·4H2The quality of O, specific parameter changes are shown in Table 1, and the coal direct liquefaction catalyst S5 is obtained.
Example 6
The procedure is as in example 1, except that Zr (SO) is not added4)2·4H2O, specific parameter changes are shown in Table 1, and the coal direct liquefaction catalyst S6 is obtained.
Example 7
According to the method of example 1, except for changing the quality of the pulverized coal, the specific parameters are listed in table 1, the direct coal liquefaction catalyst S7 was obtained.
Example 8
According to the method of example 1, except for changing the quality of the pulverized coal, the specific parameters are listed in table 1, the direct coal liquefaction catalyst S8 was obtained.
Example 9
Following the procedure of example 1, except that the temperature of the precipitation reaction was replaced with 60 ℃, the specific parameters are listed in table 1, the direct coal liquefaction catalyst S9 was obtained.
Example 10
According to the method of example 1, except that the pH of the reaction solution was changed to 9 and the specific parameters are shown in Table 1, the coal direct liquefaction catalyst S10 was obtained.
Example 11
According to the method of example 1, except that the pH of the reaction solution was changed to 5.8 and the specific parameters are shown in Table 1, the coal direct liquefaction catalyst S11 was obtained.
Example 12
The procedure of example 1 was followed, except that the filtered product was directly dried and ground to obtain coal direct liquefaction catalyst S12.
Comparative example 1
The procedure is as in example 1, except that ZnSO is not added4·7H2O to obtain the coal direct liquefaction catalyst D1.
Comparative example 2
The procedure is as in example 1, except that ZnSO is not added4·7H2O、Zr(SO4)2·4H2O and (NH)4)6Mo7O24·4H2And O, directly drying and grinding the filtered product to obtain the coal direct liquefaction catalyst D2.
Comparative example 3
The procedure is as in example 1, except that ZnSO is not added4·7H2O and Zr (SO)4)2·4H2And O, directly drying and grinding the filtered product to obtain the coal direct liquefaction catalyst D3.
TABLE 1
| Fe/Mo1 | Zn/Zr2 | (Fe+Mo)/(Zn+Zr)3 | Metal salt4，％ | Pulverized coal5To weight percent | |
| Example 1 | 100:1 | 1:1 | 10:1 | 5 | 40 |
| Example 2 | 16.7:1 | 1:1 | 10:1 | 5 | 40 |
| Example 3 | 250:1 | 1:1 | 10:1 | 5 | 40 |
| Example 4 | 100:1 | 3:1 | 1.67:1 | 5.4 | 40 |
| Example 5 | 100:1 | 6:1 | 40:1 | 4.5 | 40 |
| Example 6 | 100:1 | - | 20:1 | 4.7 | 40 |
| Example 7 | 100:1 | 1:1 | 10:1 | 5 | 65 |
| Example 8 | 100:1 | 1:1 | 10:1 | 5 | 20 |
| Example 9 | 100:1 | 1:1 | 10:1 | 5 | 40 |
| Example 10 | 100:1 | 1:1 | 10:1 | 5 | 40 |
| Example 11 | 100:1 | 1:1 | 10:1 | 5 | 40 |
| Example 12 | 100:1 | 1:1 | 10:1 | 5 | 40 |
Note: 1-molar ratio of iron element to molybdenum element in the main active component; 2-refers to the molar ratio of zinc element to zirconium element in the auxiliary agent component; 3-means the molar ratio of the main active ingredient to the auxiliary ingredient, wherein the main active ingredient is calculated by the total mole of the iron element and the molybdenum element, and the auxiliary ingredient is calculated by the total mole of the zinc element and the zirconium element; 4-refers to the mass concentration of the metal salt in the metal salt solution, wherein the metal salt is calculated by the total mass of iron ions, zinc ions and zirconium ions; 5-refers to the content of the coal dust based on the total weight of the direct coal liquefaction catalyst.
Test example
The direct coal liquefaction catalysts prepared in examples 1 to 12 and comparative examples 1 to 3 were subjected to a direct coal liquefaction reaction under test conditions:
dry coal (Shendong coal, analysis is listed in Table 2) and direct coal liquefaction catalysts (S1-S12 and D1-D3) are respectively added into a 500mL high-pressure autoclave coal liquefaction reaction kettle;
distillate oil with the coal liquefaction distillation range of 200-430 ℃ is taken as a solvent, the adding amount of the solvent is 42g, and 0.32g of sulfur powder is added. The initial pressure of the cold hydrogen in the autoclave reaction is 10MPa, the temperature is kept at 450 ℃ for 1h, the reaction is rapidly cooled after the reaction is finished, a gas sample is taken to measure the composition of the reaction, the liquid phase and the solid phase after the reaction are collected, soxhlet extraction is respectively carried out for 48h by n-hexane and tetrahydrofuran, the extraction residues are burnt to ash, the coal conversion rate, the oil yield, the gas yield and the asphalt yield are obtained by calculation, and the coal liquefaction result is specifically shown in Table 3.
TABLE 2
TABLE 3
Note: 6-weight ratio of coal direct liquefaction catalyst to dry coal, and the coal direct liquefaction catalyst is based on the total weight of iron element and molybdenum element in the main active component.
According to the data in tables 1 and 3, the direct coal liquefaction catalyst provided by the invention has excellent direct coal liquefaction catalytic performance, and compared with the traditional coal powder loaded iron catalyst, the conversion rate and the oil yield of coal can be greatly improved under the condition that the dosage is reduced by half, so that the catalyst and the preparation method thereof provided by the invention fully play the catalytic action of two active elements, namely iron and molybdenum, and generate a synergistic catalytic effect.
Compared with the comparative example 1, the Zn element is introduced into the example 1, so that the conversion rate and the oil yield of the coal liquefaction catalyst are improved; compared with the comparative example 2 using 2 times of iron amount, the oil yield of the direct coal liquefaction catalyst prepared in the example 1 is improved by 9.5 percentage points; compared with the comparative example 3 in which the active ingredient Mo is added but no auxiliary agent is added, the oil yield of the coal direct liquefaction catalyst prepared in the example 1 is improved by 10 percent.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, numerous simple modifications can be made to the technical solution of the invention, including combinations of the individual specific technical features in any suitable way. The invention is not described in detail in order to avoid unnecessary repetition. Such simple modifications and combinations should be considered within the scope of the present disclosure as well.
Claims (10)
1. The direct coal liquefaction catalyst is characterized by comprising a carrier and an active component, wherein the active component comprises a main active component and an auxiliary component, and the carrier is coal dust;
wherein the main active component comprises iron element and molybdenum element, and the auxiliary component comprises zinc element and optional zirconium element.
2. The catalyst according to claim 1, wherein the molar ratio of the main active component to the auxiliary component in the active component is 1-50:1, preferably 2-40: 1.
3. The catalyst according to claim 1 or 2, wherein the molar ratio of the iron element to the molybdenum element in the main active component is 15-250:1, preferably 30-200: 1;
preferably, in the auxiliary agent component, the molar ratio of the zinc element to the zirconium element is 1-10:0-1, preferably 1-8: 1.
4. A catalyst according to any one of claims 1 to 3, wherein the support is present in an amount of from 20 to 80 wt%, preferably from 30 to 70 wt%, based on the total weight of the catalyst;
preferably, the average particle size of the pulverized coal is less than or equal to 150 μm, and preferably, the average particle size is less than or equal to 80 μm.
5. The catalyst according to any one of claims 1 to 4, wherein the particle size of the catalyst is 80 μm or less.
6. A preparation method of a coal direct liquefaction catalyst is characterized by comprising the following steps:
(1) mixing iron salt, zinc salt, optional zirconium salt and deionized water to obtain a metal salt solution, and dissolving molybdenum salt in ammonia water to obtain an ammonia solution containing molybdenum;
(2) carrying out precipitation reaction on the molybdenum-containing ammonia solution and a metal salt solution, and adding ammonia water to adjust the pH value of the mixed solution to 5.5-9 to obtain precipitation slurry;
(3) mixing the precipitation slurry with coal powder to obtain a catalyst precursor;
(4) and sequentially filtering, drying and grinding the catalyst precursor to obtain the direct coal liquefaction catalyst.
7. The method according to claim 6, wherein the metal salt solution has a metal salt mass concentration of 1-15%, preferably 3-10%, based on the total mass of iron, zinc and zirconium ions;
preferably, the metal salt is selected from sulfates and/or nitrates of at least one of iron, zinc and zirconium;
preferably, the molybdenum salt is a soluble salt containing molybdenum, preferably ammonium molybdate.
8. The method of claim 6 or 7, wherein the conditions of the precipitation reaction comprise: the temperature is 10-40 ℃, preferably 15-25 ℃; the time is 0.1 to 5 hours, preferably 0.5 to 3 hours;
preferably, the method further comprises: and washing the filtered filter cake, and then sequentially drying and grinding.
9. Use of the direct coal liquefaction catalyst of any one of claims 1 to 5 and/or the direct coal liquefaction catalyst produced by the method of any one of claims 6 to 8 in direct coal liquefaction.
10. A direct coal liquefaction method, which carries out direct coal liquefaction by using the direct coal liquefaction catalyst of any one of claims 1 to 5 and/or the direct coal liquefaction catalyst prepared by the method of any one of claims 6 to 8;
wherein the conditions for direct coal liquefaction comprise: the reaction temperature is 400-500 ℃, preferably 440-460 ℃; the reaction pressure is 5-30MPa, preferably 15-25 MPa; the retention time is 1-10h, preferably 1-5 h;
preferably, the weight ratio of the coal direct liquefaction catalyst to dry coal is 0.2-0.8: 100, wherein the first and second substrates are, among others,
the direct coal liquefaction catalyst is based on the total weight of iron and molybdenum in the main active component.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS56118741A (en) * | 1980-02-26 | 1981-09-17 | Yamagata Daigaku | Catalyst for direct liquefying reaction of coal |
| CN103769108A (en) * | 2014-03-05 | 2014-05-07 | 神华集团有限责任公司 | Method for simultaneously preparing Fischer-tropsch iron-based catalyst and direct coal liquefaction catalyst |
| CN109926057A (en) * | 2019-03-14 | 2019-06-25 | 李大鹏 | A kind of Fe (III) base catalyst and its preparation method and application |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS56118741A (en) * | 1980-02-26 | 1981-09-17 | Yamagata Daigaku | Catalyst for direct liquefying reaction of coal |
| CN103769108A (en) * | 2014-03-05 | 2014-05-07 | 神华集团有限责任公司 | Method for simultaneously preparing Fischer-tropsch iron-based catalyst and direct coal liquefaction catalyst |
| CN109926057A (en) * | 2019-03-14 | 2019-06-25 | 李大鹏 | A kind of Fe (III) base catalyst and its preparation method and application |
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