CN114433168A - Catalyst for biological coke gasification reaction and biological coke gasification raw material - Google Patents
Catalyst for biological coke gasification reaction and biological coke gasification raw material Download PDFInfo
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- CN114433168A CN114433168A CN202011197972.6A CN202011197972A CN114433168A CN 114433168 A CN114433168 A CN 114433168A CN 202011197972 A CN202011197972 A CN 202011197972A CN 114433168 A CN114433168 A CN 114433168A
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- China
- Prior art keywords
- sulfate
- biological coke
- gasification
- raw material
- biological
- Prior art date
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- 239000000571 coke Substances 0.000 title claims abstract description 122
- 238000002309 gasification Methods 0.000 title claims abstract description 104
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 101
- 239000003054 catalyst Substances 0.000 title claims abstract description 49
- 239000002994 raw material Substances 0.000 title claims abstract description 45
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 42
- -1 transition metal salt Chemical class 0.000 claims abstract description 33
- 229910052936 alkali metal sulfate Inorganic materials 0.000 claims abstract description 32
- 238000002156 mixing Methods 0.000 claims abstract description 20
- 238000001035 drying Methods 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 41
- 238000000034 method Methods 0.000 claims description 29
- 239000007789 gas Substances 0.000 claims description 28
- 239000001257 hydrogen Substances 0.000 claims description 22
- 229910052739 hydrogen Inorganic materials 0.000 claims description 22
- 230000003197 catalytic effect Effects 0.000 claims description 17
- 230000008569 process Effects 0.000 claims description 17
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 16
- 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 claims description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 14
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 14
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 13
- 229960002089 ferrous chloride Drugs 0.000 claims description 12
- 239000011790 ferrous sulphate Substances 0.000 claims description 12
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 12
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- 150000003624 transition metals Chemical group 0.000 claims description 10
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 claims description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 8
- FLJPGEWQYJVDPF-UHFFFAOYSA-L caesium sulfate Chemical compound [Cs+].[Cs+].[O-]S([O-])(=O)=O FLJPGEWQYJVDPF-UHFFFAOYSA-L 0.000 claims description 8
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 8
- 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 claims description 8
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 8
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 8
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 8
- 235000011151 potassium sulphates Nutrition 0.000 claims description 8
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 8
- 235000011152 sodium sulphate Nutrition 0.000 claims description 8
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 claims description 8
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 8
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 8
- 229910052742 iron Inorganic materials 0.000 claims description 7
- 229910002651 NO3 Inorganic materials 0.000 claims description 6
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 6
- 150000002431 hydrogen Chemical class 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 6
- 230000004913 activation Effects 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 5
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- IXHYSEYEWBXTCP-UHFFFAOYSA-L [Fr+].[Fr+].[O-]S([O-])(=O)=O Chemical compound [Fr+].[Fr+].[O-]S([O-])(=O)=O IXHYSEYEWBXTCP-UHFFFAOYSA-L 0.000 claims description 4
- 239000012159 carrier gas Substances 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 4
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 4
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 4
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 4
- 229940044175 cobalt sulfate Drugs 0.000 claims description 4
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 4
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 4
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 4
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 4
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 4
- 229910000344 rubidium sulfate Inorganic materials 0.000 claims description 4
- GANPIEKBSASAOC-UHFFFAOYSA-L rubidium(1+);sulfate Chemical compound [Rb+].[Rb+].[O-]S([O-])(=O)=O GANPIEKBSASAOC-UHFFFAOYSA-L 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- 239000011592 zinc chloride Substances 0.000 claims description 4
- 235000005074 zinc chloride Nutrition 0.000 claims description 4
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 4
- 229960001763 zinc sulfate Drugs 0.000 claims description 4
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 3
- 238000010521 absorption reaction Methods 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 13
- 230000015572 biosynthetic process Effects 0.000 abstract description 7
- 238000003786 synthesis reaction Methods 0.000 abstract description 7
- 239000002028 Biomass Substances 0.000 description 17
- 239000002245 particle Substances 0.000 description 13
- 238000005303 weighing Methods 0.000 description 12
- 230000004907 flux Effects 0.000 description 11
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 8
- 230000003213 activating effect Effects 0.000 description 8
- 238000007580 dry-mixing Methods 0.000 description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 8
- 238000001994 activation Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 238000011068 loading method Methods 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 230000005496 eutectics Effects 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- 238000003763 carbonization Methods 0.000 description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 description 4
- 238000000197 pyrolysis Methods 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 241000209094 Oryza Species 0.000 description 3
- 235000007164 Oryza sativa Nutrition 0.000 description 3
- 229910052977 alkali metal sulfide Inorganic materials 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 235000009566 rice Nutrition 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- 241000723382 Corylus Species 0.000 description 2
- 235000001543 Corylus americana Nutrition 0.000 description 2
- 235000007466 Corylus avellana Nutrition 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 229910001508 alkali metal halide Inorganic materials 0.000 description 2
- 150000008045 alkali metal halides Chemical class 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000012265 solid product Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000011686 zinc sulphate Substances 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 description 1
- 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 description 1
- 229910021577 Iron(II) chloride Inorganic materials 0.000 description 1
- 241000218657 Picea Species 0.000 description 1
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 1
- 235000011613 Pinus brutia Nutrition 0.000 description 1
- 241000018646 Pinus brutia Species 0.000 description 1
- 235000008582 Pinus sylvestris Nutrition 0.000 description 1
- 241000218626 Pinus sylvestris Species 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001339 alkali metal compounds Chemical class 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 239000010828 animal waste Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000007405 data analysis Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 210000003608 fece Anatomy 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000013081 microcrystal Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001839 pinus sylvestris Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 229910000859 α-Fe Inorganic materials 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
- B01J27/25—Nitrates
-
- 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
- B01J27/053—Sulfates
-
- 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
- B01J27/053—Sulfates
- B01J27/055—Sulfates with alkali metals, copper, gold or silver
-
- 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
- B01J27/128—Halogens; Compounds thereof with iron group metals or platinum group metals
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J2300/00—Details of gasification processes
- C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
- C10J2300/0913—Carbonaceous raw material
- C10J2300/0916—Biomass
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J2300/00—Details of gasification processes
- C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
- C10J2300/0953—Gasifying agents
- C10J2300/0973—Water
- C10J2300/0976—Water as steam
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J2300/00—Details of gasification processes
- C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
- C10J2300/0983—Additives
- C10J2300/0986—Catalysts
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention discloses a catalyst for biological coke gasification reaction and a biological coke gasification raw material. The raw material for gasifying the biological coke comprises biological coke, alkali metal sulfate and transition metal salt. And mixing the biological coke raw material, the alkali metal sulfate and the transition metal salt, uniformly mixing, and drying to obtain the biological coke gasification raw material. The catalyst for the gasification reaction of the biological coke improves the gasification reaction activity of the biological coke, converts the low-value biological coke into a synthesis gas product with high calorific value, realizes high-value utilization of the biological coke and widens the utilization path of the biological coke.
Description
Technical Field
The invention relates to the field of biological coke gasification, in particular to a biological coke gasification catalyst and a biological coke catalytic raw material.
Background
The biomass is a crystallization energy source for realizing zero emission of carbon dioxide, can effectively reduce the emission of greenhouse gases and harmful gases, and links the irreversible pollution to the world environment caused by the use of fossil fuels. On the other hand, the biomass reserves are abundant and can be regenerated, and the total amount of biomass growing on the earth every year is 1400-1800 hundred million tons, which is equivalent to 10 times of the total energy consumption in the world at present. The biomass hydrogen production technology is developed, so that the resource treasure house can be effectively developed and utilized, and the strategic significance of sustainable development is achieved.
The energy of the biomass can be efficiently converted by cracking or gasifying the biomass, and the development and utilization of the biomass energy are facilitated. The synthesis gas composed of the gaseous products hydrogen and carbon monoxide is an important chemical raw material, and can be used as an intermediate for refining or synthesizing various high-quality liquid fuels and chemicals, such as hydrogen, methanol, dimethyl ether, various Fischer-Tropsch fuels and the like. However, the gasification furnace is very demanding in terms of the preparation of synthesis gas by direct steam gasification of biomass, and the crude synthesis gas produced at the same time has high tar content and requires a very complicated gas purification process.
The biological coke is a solid product generated by the carbonization reaction of residual residues after the biomass is heated and decomposed under the anaerobic or anoxic condition and is volatilized and analyzed. Because the biomass raw material contains a large amount of volatile components, a porous structure is formed in the biomass and on the surface of the biomass in the precipitation process, compared with the biomass raw material, the content of the volatile components and the oxygen content in the biomass coke are greatly reduced, and a large amount of fixed carbon components are enriched, so the biomass coke has good reaction activity and is a high-quality gasification raw material.
When the biological coke is gasified, the gasifying agent is generally carbon dioxide or water vapor, the carbon dioxide gasification of the biological coke needs higher temperature, and the reaction conditions are more severe. When the gasifying agent is steam, the steam can directly react with hot carbon and can also react with hydrocarbon to generate water-gas shift reaction to convert C in the semicoke into gases such as H2, CO2 and CH4, and the gasified gas has a single composition and hardly contains tar components.
When the biological coke is directly subjected to gasification reaction with steam, the reaction activity is low, a gasification catalyst needs to be added to improve the reaction activity of the biological coke, the alkali metal catalyst is the catalyst which has the highest promotion range of the catalytic gasification performance of the biological coke so far, and particularly the catalytic effect of potassium carbonate is the most remarkable. Although the potassium carbonate has better catalytic activity when being used as a biological coke gasification catalyst, the expensive price of the potassium carbonate is a main problem of high cost of the catalytic gasification of the biological coke, and the scale use of the potassium catalyst is also a difficult problem. The cheap alkali metal compounds such as alkali metal halide, alkali metal sulfate and the like have a certain catalytic action on the biological coke steam gasification, but the catalytic activity is far lower than that of potassium carbonate, the conversion rate of the biological coke steam gasification reaction is low, and therefore, the search for an efficient and cheap catalyst becomes a key problem for accelerating the deep utilization of the biological coke gasification technology.
Disclosure of Invention
Aiming at the technical problems in the prior art, the invention aims to provide a catalyst for biological coke gasification reaction and a biological coke gasification raw material, which take a catalytic material with low price and wide source as a biological coke gasification catalyst to realize the improvement of the activity of the biological coke gasification reaction.
The first aspect of the present invention provides a catalyst for a gasification reaction of a biocoke, which comprises an alkali metal sulfate and a transition metal salt.
In the catalyst for the biological coke gasification reaction, the mass ratio of the alkali metal sulfate to the transition metal salt is 10: 1-2: 1, preferably 9: 1-3: 1.
In the above catalyst for biological coke gasification reaction, the alkali metal sulfate may be one or more selected from the group consisting of lithium sulfate, sodium sulfate, potassium sulfate, rubidium sulfate, cesium sulfate, and francium sulfate, and preferably one or more selected from the group consisting of lithium sulfate, sodium sulfate, and potassium sulfate.
In the catalyst for biological coke gasification reaction, the transition metal salt is a transition metal inorganic salt, and may be one or more of nitrate, sulfate and hydrochloride, the transition metal is one or more of iron, copper, zinc, cobalt and nickel, and more specifically, the transition metal salt may be one or more selected from nickel nitrate, ferric nitrate, cobalt nitrate, copper nitrate, zinc nitrate, ferric chloride, ferrous chloride, nickel chloride, cobalt chloride, copper chloride, zinc chloride, ferric sulfate, ferrous sulfate, nickel sulfate, cobalt sulfate and zinc sulfate, preferably one or more selected from ferric chloride, ferrous chloride, ferric nitrate, ferric sulfate and ferrous sulfate, and further preferably one or more selected from ferrous chloride and ferrous sulfate.
In a second aspect, the invention provides a biological char gasification feedstock comprising a biological char feedstock, an alkali metal sulfate, and a transition metal salt.
Further, the particle size of the biological coke raw material is less than 2mm, and the biological coke raw material can be a solid product obtained by performing pyrolysis or and liquefaction or carbonization on biomass such as agricultural residues, forestry wastes, household garbage, waste plastics and animal wastes.
Further, the alkali metal sulfate may be one or more selected from lithium sulfate, sodium sulfate, potassium sulfate, rubidium sulfate, cesium sulfate, and francium sulfate, and preferably, one or more selected from lithium sulfate, sodium sulfate, and potassium sulfate.
Further, the transition metal salt is a transition metal inorganic salt, and may be one or more of nitrate, sulfate and hydrochloride, the transition metal is one or more of iron, copper, zinc, cobalt and nickel, and more specifically, the transition metal salt may be one or more selected from nickel nitrate, ferric nitrate, cobalt nitrate, copper nitrate, zinc nitrate, ferric chloride, ferrous chloride, nickel chloride, cobalt chloride, copper chloride, zinc chloride, ferric sulfate, ferrous sulfate, nickel sulfate, cobalt sulfate, copper sulfate and zinc sulfate, preferably is one or more selected from ferric chloride, ferrous chloride, ferric nitrate, ferric sulfate and ferrous sulfate, and further preferably is one or more selected from ferrous chloride and ferrous sulfate.
Further, in the raw material for gasifying the biological coke, the mass ratio of the sum of the alkali metal sulfate and the transition metal salt to the raw material for gasifying the biological coke is 40-3: 97-60, wherein the mass ratio of the alkali metal sulfate to the transition metal salt is 10: 1-2: 1, preferably 9: 1-3: 1.
The third aspect of the invention provides a preparation method of a biological coke gasification raw material, which comprises the steps of mixing the biological coke raw material, alkali metal sulfate and transition metal salt, uniformly mixing, and drying to obtain the biological coke gasification raw material.
Further, in the preparation method, the drying temperature is 100-120 ℃.
Furthermore, in the above preparation method, the mixing may be any means capable of achieving uniform mixing of solid phase materials in the prior art, such as grinding and stirring.
In a fourth aspect of the present invention, there is provided a method for producing a raw material for gasification of biocoke according to another embodiment, wherein an aqueous solution containing alkali metal sulfate and a transition metal salt is prepared by mixing alkali metal sulfate, a transition metal salt and water, and then the aqueous solution is mixed with biocoke, and the mixture is uniformly mixed and dried to obtain a raw material for gasification of biocoke.
Further, in the preparation method, the addition amount of the water is the saturated water absorption amount of the equivalent ratio of the biological coke, and the addition amount of the water is 1.5-2 g of water/g of biological coke according to the type of the biological coke and the air humidity.
Further, in the preparation method, the drying temperature is 60-120 ℃.
According to the fifth aspect of the invention, the biological coke gasification raw material prepared in the above way is activated in a reducing atmosphere, and then contacts with steam in a gasification furnace to perform gasification reaction.
In the biological coke gasification process, the reducing atmosphere can be a gas containing hydrogen, specifically a mixed gas of hydrogen, hydrogen and a carrier gas, the carrier gas is one or more of helium, nitrogen and water vapor, and the volume fraction of hydrogen in the mixed gas is 5-50%.
In the biological coke gasification process, the activation treatment temperature is 200-750 ℃, and preferably 300-750 ℃.
In the biological coke gasification process, the gasification reaction temperature is 700-950 ℃.
In the biological coke gasification process, the mass ratio of the water vapor to the biological coke raw material in the biological coke gasification reaction process is 0.1-10, preferably 0.2-8.
Compared with the prior art, the catalyst for the biological coke gasification reaction and the biological coke gasification raw material provided by the invention have the following technical effects:
1. the catalyst for the biological coke gasification reaction provided by the invention comprises two low-cost catalyst raw materials of transition metal salt and alkali metal sulfate, and a low-melting-point eutectic is formed in the catalyst activation process, so that the contact performance of the catalyst and a biological coke solid-solid reaction interface is improved; transition metals such as simple substance iron and the like generated in situ can accelerate the generation process of the catalytic low-melting-point eutectic, greatly improve the reaction activity of the biological coke and overcome the problem of low activity of the existing catalytic material.
2. The catalyst for the biological coke gasification reaction comprises alkali metal sulfate and transition metal salt, when the catalyst is used in the biological coke steam gasification process, the catalyst is heated to a certain temperature in a reducing atmosphere in an activation process, the alkali metal sulfate is reduced into alkali metal sulfide by hydrogen, the alkali metal sulfide and the alkali metal sulfate can form a low-melting-point eutectic in the biological coke steam gasification atmosphere, and the low-melting-point eutectic has stronger fluidity than that of the sodium carbonate or the sodium ferrite at a reaction temperature, so that the wettability and the adhesive force of the catalyst on the carbon particle surface are obviously enhanced, the contact between the catalyst and carbon microcrystals is more sufficient, the gasification conversion rate of the biological coke is greatly improved, and the steam gasification performance is improved. Furthermore, transition metal salt (such as ferric salt or ferrous salt) in the catalytic system is reduced by reducing gas or glowing biochar with strong reducibility in the activation process to generate active elementary iron under the reaction condition, the appearance of the elementary iron can obviously promote the process of reducing alkali metal sulfate to generate alkali metal sulfide, promote low-melting-point eutectic to appear at lower temperature, reduce the gasification reaction temperature, gasify the biological coke water vapor at lower temperature, greatly improve the average water conversion rate and the yield of synthesis gas, and obviously improve the gasification reaction activity of the biological coke.
3. The catalyst for the gasification reaction of the biological coke improves the gasification reaction activity of the biological coke, converts the low-value biological coke into a synthesis gas product with high calorific value, realizes high-value utilization of the biological coke and widens the utilization path of the biological coke.
4. The two catalytic raw materials of the catalyst for the gasification reaction of the biological coke are low in price and wide in source, and can be used as a waste catalyst for treatment and can also be recycled by a water-soluble method, so that the recycling of the catalyst is realized.
Detailed Description
The present invention will be described in more detail with reference to examples and comparative examples, but the scope of the present invention is not limited by the examples.
Example 1
Weighing 16g of hazelnut pyrolytic biological coke with the particle size of less than 2mm and 1.32gK2SO4、0.14g Ni(NO3)2Uniformly mixing the samples, drying at 105 ℃ for 6 hours to obtain a biological coke gasification raw material prepared by a dry mixing method, loading the samples on a microwave fixed bed reactor, and activating at 300 ℃ in a hydrogen-nitrogen (the volume fraction of hydrogen is 5%) mixed atmosphere for 10 min; introducing steam to carry out gasification reaction, wherein the reaction conditions are as follows: the temperature is 800 ℃, the pressure is normal, the flux of water is 0.35mL/min, after 40min of reaction, the average water conversion rate in the reaction process is 91%, and the yield of synthetic gas is 1117g/kg biological coke.
Example 2
Weighing 15g of rice hull pyrolysis biological coke with the particle size less than 2mm and 0.96gK2SO4、1.21gFeSO4×7H2O, mixing the above samples uniformly, and drying at 120 deg.C for 4 hrThen, the biological coke loaded with the catalyst and prepared by a dry mixing method is obtained, the sample is put into a microwave fixed bed reactor, and the catalyst is activated at 700 ℃ in a mixed atmosphere of hydrogen and nitrogen (the volume fraction of the hydrogen is 50%), wherein the activation time is 20 min; putting the sample into a microwave fixed bed reactor to carry out steam gasification reaction, wherein the reaction conditions are as follows: the temperature is 850 ℃, the pressure is normal, the flux of water is 0.5mL/min, after 50min of reaction, the average water conversion rate in the reaction process is 85%, and the yield of the synthetic gas is 1076g/kg of biological coke.
Example 3
Weighing 18g of pinus sylvestris pyrolytic biological coke with particle size less than 2mm and 9g of Na2SO4、9g CoCl2Uniformly mixing the samples, drying the samples at 115 ℃ for 5 hours to obtain a biological coke gasification raw material prepared by a dry mixing method, loading the samples on a microwave fixed bed reactor, and activating the samples at 400 ℃ in a hydrogen-nitrogen (the volume fraction of hydrogen is 30%) mixed atmosphere for 30 min; introducing steam to carry out gasification reaction, wherein the reaction conditions are as follows: the temperature is 700 ℃, the pressure is normal, the flux of water is 0.6mL/min, after 40min of reaction, the average water conversion rate in the reaction process is 46%, and the yield of the synthetic gas is 1164g/kg biological coke.
Example 4
Weighing 13g of rice hull pyrolysis biological coke with the particle size of less than 2mm and 1.67g of Na2SO4、1.63gFeCl3Uniformly mixing the samples, drying at 120 ℃ for 4 hours to obtain catalyst-loaded biological coke prepared by a dry mixing method, loading the samples into a microwave fixed bed reactor, and activating the catalyst at 700 ℃ in a hydrogen-nitrogen mixed atmosphere (the volume fraction of hydrogen is 45%), wherein the activation time is 15 min; introducing steam to carry out gasification reaction, wherein the reaction conditions are as follows: the temperature is 850 ℃, the pressure is normal, the flux of water is 0.35mL/min, after 65min of reaction, the average water conversion rate in the reaction process is 68%, and the yield of the synthetic gas is 1035g/kg biological coke.
Example 5
Weighing 12g of plastic pyrolytic biological coke with particle size less than 2mm and 0.61g K2SO4、0.72g Na2SO4、0.41g FeCl2Uniformly mixing the samples, drying at 120 ℃ for 4 hours to obtain catalyst-loaded biological coke prepared by a dry mixing method, loading the samples into a microwave fixed bed reactor, and activating the catalyst at 750 ℃ in a hydrogen-nitrogen mixed atmosphere (the volume fraction of hydrogen is 30%), wherein the activation time is 10 min; introducing steam to carry out gasification reaction, wherein the reaction conditions are as follows: the temperature is 750 ℃, the pressure is normal, the flux of water is 0.3mL/min, after 75min of reaction, the average water conversion rate in the reaction process is 71%, and the yield of the synthetic gas is 1203g/kg biological coke.
Example 6
Weighing 13g of plastic pyrolytic biological coke with particle size less than 2mm and 1.05g K2SO4、2.1gFe（NO3）3×9H2O, uniformly mixing the samples, drying at 120 ℃ for 4 hours to obtain catalyst-loaded biological coke prepared by a dry mixing method, putting the samples on a microwave fixed bed reactor, and activating at 650 ℃ in a hydrogen-nitrogen (the volume fraction of hydrogen is 50%) mixed atmosphere for 10 min; introducing steam to carry out gasification reaction, wherein the reaction conditions are as follows: the temperature is 900 ℃, the pressure is normal, the flux of water is 0.5mL/min, after 75min of reaction, the average water conversion rate in the reaction process is 78%, and the yield of the synthetic gas is 1131g/kg biological coke.
Example 7
Weighing 1gK2SO4、0.16gZnSO445g of water and stirring the mixture fully to obtain the K-containing mixture2SO4And ZnSO4Then 30g of pine carbonized biological coke with the particle size less than 2mm and K are weighed2SO4And ZnSO4Mixing the solutions, and stirring for 6 hours; finally, drying the uniformly mixed materials at 80 ℃ for 10 hours to obtain a biological coke catalytic raw material sample prepared by an impregnation method, putting the sample on a microwave fixed bed reactor, and activating at 300 ℃ for 5min under a hydrogen-nitrogen (hydrogen volume fraction is 5%) mixed atmosphere; introducing steam to carry out gasification reaction, wherein the reaction conditions are as follows: the temperature is 750 ℃, the pressure is normal, the flux of water is 0.3mL/min, after 52min of reaction, the average water conversion rate in the reaction process is 56 percent,the synthesis gas yield was 329g/kg biocoke.
Example 8
Weighing 8gLi2SO4、0.89gCu(NO3)232g of water, and stirring the mixture fully to obtain the Li-containing material2SO4And Cu (NO)3)2Then weighing 16g of spruce carbonized biological coke with the particle size less than 2mm and Li2SO4And Cu (NO)3)2Mixing the solutions, and stirring for 6 hours; finally, drying the uniformly mixed materials at 60 ℃ for 12 hours to obtain a biological coke catalytic raw material sample prepared by an impregnation method, putting the sample on a microwave fixed bed reactor, and activating at 450 ℃ for 15min under a hydrogen-nitrogen (the volume fraction of hydrogen is 10%) mixed atmosphere; introducing steam to carry out gasification reaction, wherein the reaction conditions are as follows: the temperature is 950 ℃, the pressure is normal, the flux of water is 0.3mL/min, after 45min of reaction, the average water conversion rate in the reaction process is 95%, and the yield of the synthetic gas is 1301g/kg of biological coke.
Comparative example 1
Weighing 15g of cow dung pyrolytic biological coke with the particle size smaller than 2mm, and carrying out steam gasification on a microwave fixed bed reactor, wherein the reaction conditions are as follows: the temperature is 700 ℃, the pressure is normal, the flux of water is 0.2mL/min, the average water conversion rate in the reaction process of reacting for 70min is 9 percent, and the yield of the synthetic gas is 52g/kg biological coke.
Comparative example 2
Weighing 16g of hazelnut pyrolytic biological coke with the particle size of less than 2mm and 1.32gK2SO4Uniformly mixing the samples, drying at 105 ℃ for 6 hours to obtain a biological coke gasification raw material prepared by a dry mixing method, loading the samples into a microwave fixed bed reactor, and introducing water vapor to carry out gasification reaction under the reaction conditions of: the temperature is 800 ℃, the pressure is normal, the flux of water is 0.35mL/min, after 40min of reaction, the average water conversion rate in the reaction process is 73%, and the yield of the synthetic gas is 820g/kg biological coke.
Comparative example 3
Weighing 15g of rice hull pyrolysis biological coke with the particle size less than 2mm and 1.21g of FeSO4×7H2O, mixing the above samples uniformly, and thenDrying at 120 ℃ for 4 hours to obtain catalyst-loaded biological coke prepared by a dry mixing method, loading the sample into a microwave fixed bed reactor, and activating the catalyst at 700 ℃ in a hydrogen-nitrogen (the volume fraction of hydrogen is 50%) mixed atmosphere for 20 min; putting the sample into a microwave fixed bed reactor to carry out steam gasification reaction, wherein the reaction conditions are as follows: the temperature is 850 ℃, the pressure is normal, the flux of water is 0.5mL/min, after 50min of reaction, the average water conversion rate in the reaction process is 22%, and the yield of the synthetic gas is 316g/kg biological coke.
It can be seen from the data analysis of the examples and comparative examples that the gasification activity of the biocoke is improved when the alkali metal sulfate is added as the catalyst alone in the process of steam gasification of the biocoke, and the gasification activity of the biocoke is reduced when the transition metal salt is added as the catalyst alone. According to the invention, two low-cost catalyst raw materials of transition metal salt and alkali metal sulfate are adopted in the biological coke gasification process, the transition metal salt is used for catalyzing biomass carbonization reaction, and substances such as transition metal oxide, transition metal simple substance and the like generated in the carbonization reaction continuously interact with the alkali metal sulfate in the biological coke gasification process, so that the biological coke steam gasification activity of the alkali metal sulfate is greatly improved, the problem of low catalytic activity of a cheap alkali metal halide catalytic material is solved, and the reaction cost is greatly reduced.
Claims (20)
1. A catalyst for a bio-char gasification reaction, the catalyst comprising an alkali metal sulfate and a transition metal salt.
2. The catalyst for a bio-char gasification reaction according to claim 1, wherein: the alkali metal sulfate is one or more selected from lithium sulfate, sodium sulfate, potassium sulfate, rubidium sulfate, cesium sulfate and francium sulfate, preferably one or more selected from lithium sulfate, sodium sulfate and potassium sulfate.
3. The catalyst for a bio-char gasification reaction according to claim 1, wherein: the transition metal salt is transition metal inorganic salt, specifically one or more of nitrate, sulfate and hydrochloride, and the transition metal is one or more of iron, copper, zinc, cobalt and nickel.
4. The catalyst for a bio-char gasification reaction according to claim 1, wherein: the transition metal salt is one or more selected from nickel nitrate, ferric nitrate, cobalt nitrate, copper nitrate, zinc nitrate, ferric trichloride, ferrous chloride, nickel chloride, cobalt chloride, copper chloride, zinc chloride, ferric sulfate, ferrous sulfate, nickel sulfate, cobalt sulfate, copper sulfate and zinc sulfate, preferably one or more selected from ferric trichloride, ferrous chloride, ferric nitrate, ferric sulfate and ferrous sulfate, and further preferably one or more selected from ferrous chloride and ferrous sulfate.
5. The catalyst for a bio-char gasification reaction according to claim 1, wherein: the mass ratio of the alkali metal sulfate to the transition metal salt is 10: 1-2: 1, preferably 9: 1-3: 1.
6. A biocoke gasification raw material, the gasification raw material comprises a biocoke raw material, alkali metal sulfate and transition metal salt.
7. The bio-char gasification feedstock of claim 6, wherein: the alkali metal sulfate is one or more selected from lithium sulfate, sodium sulfate, potassium sulfate, rubidium sulfate, cesium sulfate and francium sulfate, and preferably one or more selected from lithium sulfate, sodium sulfate and potassium sulfate.
8. The bio-char gasification feedstock of claim 6, wherein: the transition metal salt is transition metal inorganic salt, specifically one or more of nitrate, sulfate and hydrochloride, and the transition metal is one or more of iron, copper, zinc, cobalt and nickel.
9. The bio-char gasification feedstock of claim 6, wherein: the transition metal salt is one or more selected from nickel nitrate, ferric nitrate, cobalt nitrate, copper nitrate, zinc nitrate, ferric trichloride, ferrous chloride, nickel chloride, cobalt chloride, copper chloride, zinc chloride, ferric sulfate, ferrous sulfate, nickel sulfate, cobalt sulfate, copper sulfate and zinc sulfate, preferably one or more selected from ferric trichloride, ferrous chloride, ferric nitrate, ferric sulfate and ferrous sulfate, and further preferably one or more selected from ferrous chloride and ferrous sulfate.
10. The bio-char gasification feedstock of claim 6, wherein: in the biological coke gasification raw material, the mass ratio of the sum of the alkali metal sulfate and the transition metal salt to the biological coke raw material is 40-3: 97-60, wherein the mass ratio of the alkali metal sulfate to the transition metal salt is 10: 1-2: 1, preferably 9: 1-3: 1.
11. The method for producing the biological coke gasification raw material according to any one of claims 6 to 10, wherein the biological coke raw material, the alkali metal sulfate and the transition metal salt are mixed, mixed uniformly and dried to obtain the biological coke gasification raw material.
12. The method for producing a biocoke raw material as set forth in claim 11, wherein: the drying temperature is 100-120 ℃.
13. The method for producing the biological coke gasification raw material according to any one of claims 6 to 10, wherein the method comprises the steps of mixing alkali metal sulfate, transition metal salt and water to prepare an aqueous solution containing the alkali metal sulfate and the transition metal salt, mixing the aqueous solution with the biological coke, uniformly mixing the aqueous solution and the biological coke, and drying the mixture to obtain the biological coke catalytic raw material.
14. The method for producing a biocoke raw material as set forth in claim 13, wherein: the addition amount of the water is the saturated water absorption amount of the equivalent ratio of the biological coke, and is 1.5-2 g of water/g of biological coke according to the types of the biological coke and the air humidity.
15. The process for producing a bio-char gasification feedstock according to claim 13, wherein: the drying temperature is 60-120 ℃.
16. A biological coke gasification process, wherein the biological coke gasification raw material as claimed in any one of claims 6 to 10 is activated in a reducing atmosphere and then is contacted with steam in a gasification furnace to carry out gasification reaction.
17. The biological char gasification process of claim 16, wherein: the reducing atmosphere is a gas containing hydrogen, specifically a mixed gas of hydrogen, hydrogen and a carrier gas, the carrier gas is one or more of helium, nitrogen and water vapor, and the volume fraction of the hydrogen in the mixed gas is 5-50%.
18. The biological char gasification process of claim 16, wherein: the activation treatment temperature is 200-750 ℃, and preferably 300-750 ℃.
19. The biological char gasification process of claim 16, wherein: the gasification reaction temperature is 700-950 ℃.
20. The biological char gasification process of claim 16, wherein: the mass ratio of the water vapor to the biological coke raw material in the biological coke gasification reaction process is 0.1-10, preferably 0.2-8.
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