CN115161048A - Method for directionally preparing aromatic hydrocarbon chemicals, synthesis gas and biochar by coupling biomass pyrolysis with carbon dioxide - Google Patents
Method for directionally preparing aromatic hydrocarbon chemicals, synthesis gas and biochar by coupling biomass pyrolysis with carbon dioxide Download PDFInfo
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- CN115161048A CN115161048A CN202210775239.0A CN202210775239A CN115161048A CN 115161048 A CN115161048 A CN 115161048A CN 202210775239 A CN202210775239 A CN 202210775239A CN 115161048 A CN115161048 A CN 115161048A
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- Prior art keywords
- hours
- biomass
- temperature
- pyrolysis
- catalyst
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Links
- 239000002028 Biomass Substances 0.000 title claims abstract description 83
- 238000000197 pyrolysis Methods 0.000 title claims abstract description 79
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 239000000126 substance Substances 0.000 title claims abstract description 38
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 26
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 26
- 238000000034 method Methods 0.000 title claims abstract description 26
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 24
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 24
- 150000004945 aromatic hydrocarbons Chemical class 0.000 title claims abstract description 18
- 230000008878 coupling Effects 0.000 title claims abstract description 6
- 238000010168 coupling process Methods 0.000 title claims abstract description 6
- 238000005859 coupling reaction Methods 0.000 title claims abstract description 6
- 239000003054 catalyst Substances 0.000 claims abstract description 69
- 239000007789 gas Substances 0.000 claims abstract description 62
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 32
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000003546 flue gas Substances 0.000 claims abstract description 22
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 12
- 239000001257 hydrogen Substances 0.000 claims abstract description 11
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims description 34
- 238000001035 drying Methods 0.000 claims description 28
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical class [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 27
- 239000002808 molecular sieve Substances 0.000 claims description 25
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 24
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 24
- 229910052751 metal Inorganic materials 0.000 claims description 22
- 239000002184 metal Substances 0.000 claims description 22
- 238000001354 calcination Methods 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- QPUYECUOLPXSFR-UHFFFAOYSA-N 1-methylnaphthalene Chemical compound C1=CC=C2C(C)=CC=CC2=C1 QPUYECUOLPXSFR-UHFFFAOYSA-N 0.000 claims description 16
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical compound C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 claims description 16
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 16
- 238000012216 screening Methods 0.000 claims description 16
- 239000008367 deionised water Substances 0.000 claims description 15
- 229910021641 deionized water Inorganic materials 0.000 claims description 15
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 13
- VQKFNUFAXTZWDK-UHFFFAOYSA-N 2-Methylfuran Chemical compound CC1=CC=CO1 VQKFNUFAXTZWDK-UHFFFAOYSA-N 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 239000012266 salt solution Substances 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 10
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 8
- 239000008096 xylene Substances 0.000 claims description 8
- 239000002131 composite material Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- BWLBGMIXKSTLSX-UHFFFAOYSA-N 2-hydroxyisobutyric acid Chemical compound CC(C)(O)C(O)=O BWLBGMIXKSTLSX-UHFFFAOYSA-N 0.000 claims description 6
- 229920002488 Hemicellulose Polymers 0.000 claims description 6
- 239000001913 cellulose Substances 0.000 claims description 6
- 229920002678 cellulose Polymers 0.000 claims description 6
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 150000002431 hydrogen Chemical class 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- 229920005610 lignin Polymers 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 4
- 239000011029 spinel Substances 0.000 claims description 4
- 229910052596 spinel Inorganic materials 0.000 claims description 4
- 239000002699 waste material Substances 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- 230000032683 aging Effects 0.000 claims description 3
- 239000001099 ammonium carbonate Substances 0.000 claims description 3
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 239000012263 liquid product Substances 0.000 claims description 3
- 150000002739 metals Chemical class 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 239000011733 molybdenum Substances 0.000 claims description 3
- 239000000047 product Substances 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 2
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 239000011651 chromium Substances 0.000 claims description 2
- 238000000975 co-precipitation Methods 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052733 gallium Inorganic materials 0.000 claims description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- 238000005470 impregnation Methods 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 150000002823 nitrates Chemical class 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 239000010937 tungsten Substances 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 229910004298 SiO 2 Inorganic materials 0.000 claims 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 27
- 229910052799 carbon Inorganic materials 0.000 abstract description 27
- 230000008021 deposition Effects 0.000 abstract description 14
- 238000006243 chemical reaction Methods 0.000 abstract description 9
- 230000009467 reduction Effects 0.000 abstract description 6
- 241000282414 Homo sapiens Species 0.000 abstract description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract 1
- 230000002401 inhibitory effect Effects 0.000 abstract 1
- 125000003118 aryl group Chemical group 0.000 description 27
- 239000012075 bio-oil Substances 0.000 description 16
- 239000002994 raw material Substances 0.000 description 15
- 244000166124 Eucalyptus globulus Species 0.000 description 13
- 239000012159 carrier gas Substances 0.000 description 9
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 6
- 240000008042 Zea mays Species 0.000 description 5
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 5
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 5
- 238000005899 aromatization reaction Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 235000005822 corn Nutrition 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- 238000005336 cracking Methods 0.000 description 4
- LHGVFZTZFXWLCP-UHFFFAOYSA-N guaiacol Chemical compound COC1=CC=CC=C1O LHGVFZTZFXWLCP-UHFFFAOYSA-N 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 4
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 3
- 235000011613 Pinus brutia Nutrition 0.000 description 3
- 241000018646 Pinus brutia Species 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 238000010298 pulverizing process Methods 0.000 description 3
- 229910000314 transition metal oxide Inorganic materials 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- QGAVSDVURUSLQK-UHFFFAOYSA-N ammonium heptamolybdate Chemical compound N.N.N.N.N.N.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Mo].[Mo].[Mo].[Mo].[Mo].[Mo].[Mo] QGAVSDVURUSLQK-UHFFFAOYSA-N 0.000 description 2
- 238000007233 catalytic pyrolysis Methods 0.000 description 2
- 239000000295 fuel oil Substances 0.000 description 2
- CHPZKNULDCNCBW-UHFFFAOYSA-N gallium nitrate Chemical compound [Ga+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CHPZKNULDCNCBW-UHFFFAOYSA-N 0.000 description 2
- 229960001867 guaiacol Drugs 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
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 239000010902 straw Substances 0.000 description 2
- 238000012546 transfer Methods 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
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- 241000609240 Ambelania acida Species 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 description 1
- 235000004692 Eucalyptus globulus Nutrition 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- WHMDKBIGKVEYHS-IYEMJOQQSA-L Zinc gluconate Chemical compound [Zn+2].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O WHMDKBIGKVEYHS-IYEMJOQQSA-L 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 239000010905 bagasse Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229940044927 ceric oxide Drugs 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229940117975 chromium trioxide Drugs 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N chromium trioxide Inorganic materials O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- GAMDZJFZMJECOS-UHFFFAOYSA-N chromium(6+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Cr+6] GAMDZJFZMJECOS-UHFFFAOYSA-N 0.000 description 1
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229940044658 gallium nitrate Drugs 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 description 1
- 239000003039 volatile agent Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000011670 zinc gluconate Substances 0.000 description 1
- 229960000306 zinc gluconate Drugs 0.000 description 1
- 235000011478 zinc gluconate Nutrition 0.000 description 1
- XAEWLETZEZXLHR-UHFFFAOYSA-N zinc;dioxido(dioxo)molybdenum Chemical compound [Zn+2].[O-][Mo]([O-])(=O)=O XAEWLETZEZXLHR-UHFFFAOYSA-N 0.000 description 1
- IPCXNCATNBAPKW-UHFFFAOYSA-N zinc;hydrate Chemical compound O.[Zn] IPCXNCATNBAPKW-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
- C10B53/00—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form
- C10B53/02—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form of cellulose-containing material
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/10—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing iron group metals, noble metals or copper
- B01J29/14—Iron group metals or copper
- B01J29/146—Y-type faujasite
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/405—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
- B01J29/44—Noble metals
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
- B01J29/46—Iron group metals or copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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Abstract
The invention discloses a method for directionally preparing aromatic hydrocarbon chemicals, synthesis gas and biochar by coupling biomass pyrolysis with carbon dioxide, which adopts a bimetallic catalyst, biomass and flue gas or methane containing carbon dioxide are fed together for pyrolysis, so that the directional conversion of three components of the biomass is realized, the aromatic hydrocarbon chemicals with high yield and high selectivity are prepared, the reduction of the carbon dioxide in the flue gas or the methane is realized, the carbon dioxide is reduced into carbon monoxide, the biomass is pyrolyzed to generate hydrogen, thereby obtaining the synthesis gas, reducing the emission of the carbon dioxide, simultaneously inhibiting the generation of carbon deposition on the catalyst, and in addition, the biochar is obtained, the resource utilization of the biomass is realized, and simultaneously the climate crisis of human beings is relieved.
Description
The technical field is as follows:
the invention relates to a method for directionally preparing aromatic hydrocarbon chemicals, synthesis gas and biochar by coupling biomass pyrolysis with carbon dioxide.
The background art comprises the following steps:
biomass pyrolysis is a thermochemical conversion technique that can rapidly decompose biomass at moderate temperatures, an inert atmosphere, and high heating rates (> 1000 ℃/s) to produce condensable volatiles (bio-oil), non-condensable gases, and biochar. The biomass pyrolysis technology has the advantages of high liquid yield (60-75 wt.%), full-component utilization, strong raw material adaptability, simple process, low cost, high efficiency and the like. Although the yield of the bio-oil is high, the quality of the bio-oil is poor, and the bio-oil is mainly characterized by very complex composition, high oxygen content, low heat value and strong acidity, so that the bio-oil is difficult to further purify chemicals or directly used as fuel. Therefore, there is a need to develop new pyrolysis processes to achieve directional conversion of biomass.
At present, some related researches are carried out on the preparation of high value-added chemicals by utilizing biomass fractional pyrolysis or catalytic pyrolysis. Patent CN103396820B discloses a method for condensing and separating biomass pyrolysis products to obtain bio-oil, comprising: the biomass raw material enters a fast pyrolysis reactor, fast pyrolysis reaction is carried out for a certain time at a set temperature, the reaction product is directly condensed and condensed, and the liquid-solid separation is carried out on the condensation product to obtain bio-oil and solidified carbon, and the solidified carbon and non-condensable gas are used as fuels. This patent does not relate to the use of catalysts and the production of chemicals by directional pyrolysis. Patent CN102199435B (CN 2011100982105A) discloses a method for preparing guaiacol-rich bio-oil by catalytic pyrolysis of biomass. The method comprises the following steps: uniformly mixing the biomass raw material with a sodium carbonate aqueous solution, drying to remove free moisture, then placing in a fixed bed for cracking, and condensing a cracking distillate to obtain the biological oil rich in guaiacol. The patent does not relate to coupled pyrolysis of biomass with other feedstocks. Patent CN102618312A (CN 2012100843874A) discloses a new method for preparing fuel oil by co-pyrolysis of biomass and waste plastics, which comprises: the biomass and the waste plastics are uniformly mixed according to a certain proportion and are placed in a cracking reactor, gas generated by pyrolysis enters a refining reaction tower for catalytic modification, a modified liquid product is rectified to obtain fuel oil with different fractions, and a small amount of combustible gas and residues are returned to the cracking reactor to be combusted and used as an auxiliary heat source. The patent does not relate to the production of synthesis gas by reduction of carbon dioxide.
The invention content is as follows:
the invention aims to provide a method for directionally preparing aromatic hydrocarbon chemicals, synthesis gas and biochar by biomass pyrolysis coupled with carbon dioxide, which is characterized in that a bimetallic catalyst is adopted, biomass and flue gas or methane containing carbon dioxide are subjected to co-feeding pyrolysis to realize biomass three-component directional conversion, the aromatic hydrocarbon chemicals with high yield and high selectivity are prepared, the reduction of carbon dioxide in the flue gas or methane is realized at the same time, the aromatic hydrocarbon chemicals are reduced into carbon monoxide, the biomass is pyrolyzed to generate hydrogen, the synthesis gas is obtained, the emission of the carbon dioxide is reduced, the generation of carbon deposition on the catalyst is inhibited, the biochar is obtained, the resource utilization of the biomass is realized, and the climate crisis of human beings is relieved at the same time.
The invention is realized by the following technical scheme:
a method for directionally preparing aromatic hydrocarbon chemicals, synthesis gas and biochar by coupling biomass pyrolysis with carbon dioxide comprises the following steps:
1) Preparing bimetallic catalyst, tabletting, crushing and screening to 20-80 mesh; the bimetallic catalyst is a bimetallic modified molecular sieve catalyst or a bimetallic modified spinel and molecular sieve composite catalyst, the metal is two of molybdenum, iron, gallium, zinc, nickel, copper, tungsten, cobalt, chromium, titanium, cerium, ruthenium, zirconium, aluminum, platinum or silver, the metal load accounts for 0.2-5% of the mass of the molecular sieve, the molecular sieve is any one of HZSM-5, HY @ HZSM-5 and HZSM-5@ HY, and SiO is 2 /Al 2 O 3 =2-120; HY @ HZSM-5 and HZSM-5@ HY are core-shell structure molecular sieves, HY @ HZSM-5 represents a composite molecular sieve with HY as a core and HZSM-5 as a shell; HZSM-5@ HY is the opposite, and represents the composite molecular sieve taking HZSM-5 as the core and HY as the shell;
2) Crushing and screening biomass until the particle size is less than 1cm;
3) Putting the prepared catalyst into a reactor, adding the screened biomass into the reactor, introducing flue gas or methane, pyrolyzing at 500-750 ℃, preferably at 600-700 ℃, directionally converting cellulose, hemicellulose and lignin in the biomass into aromatic hydrocarbons such as benzene, toluene, xylene, indene, naphthalene, methylnaphthalene and the like or derivatives thereof, condensing and collecting steam generated by fast pyrolysis, wherein the condensing temperature is-45 to-40 ℃, the obtained liquid product is the prepared aromatic hydrocarbon chemical, and the uncondensable pyrolysis gas is rich in carbon monoxide and hydrogen and is used as synthesis gas; the solid produced is biochar.
The preparation method of the bimetallic catalyst adopts an impregnation method or a coprecipitation method and comprises the following steps:
dissolving the salt of the metal A in deionized water, adding the mixture into a molecular sieve after uniformly stirring, stirring for 8 to 16 hours at the temperature of between 40 and 80 ℃, then transferring the mixture into an oven, drying for 12 hours at the temperature of 105 ℃, calcining for 2 to 5 hours at the temperature of between 500 and 700 ℃, then adding the salt solution of the metal B, stirring for 8 to 16 hours at the temperature of between 40 and 80 ℃, then transferring the mixture into the oven, drying for 12 hours at the temperature of 105 ℃, and calcining for 2 to 5 hours at the temperature of between 450 and 700 ℃;
or dissolving hydroxide of metal A in 2-hydroxyisobutyric acid, adding oxide of metal B and water, stirring uniformly at 100 ℃, transferring into a molecular sieve, stirring for 8-16 hours at 60-80 ℃, transferring into an oven, drying for 12 hours at 105 ℃, and calcining for 2-5 hours at 450-700 ℃;
or, the salt solution of the metal A and the salt solution of the metal B or the oxide are evenly stirred at the temperature of 60-100 ℃, then are transferred into a molecular sieve, are stirred for 8-16 hours at the temperature of 40-80 ℃, are transferred into an oven, are dried for 12 hours at the temperature of 105 ℃, and are calcined for 2-5 hours at the temperature of 450-700 ℃;
or the salt solution of the metal A and the salt solution or the oxide of the metal B are stirred evenly at the temperature of 60-100 ℃, then are directly filtered, dried at the temperature of 90 ℃, calcined at the temperature of 450-700 ℃ and then are mechanically mixed with the molecular sieve;
or dissolving nitrates of the metals A and B in deionized water according to a certain proportion, uniformly stirring at 65-75 ℃, adding ammonia water or ammonium carbonate solution, adjusting the pH to 7-8, aging at 60-80 ℃ for 1-5 hours, filtering, washing, drying, calcining at 450-1000 ℃ for 2-5 hours, and mixing with a molecular sieve to obtain the composite catalyst, wherein the proper particle size of the catalyst is 40-60 meshes.
The bimetallic catalyst has better aromatization capacity, hydrogen transfer capacity and carbon deposition resistance, mainly promotes the directional conversion and carbon dioxide reduction of biomass, and the transition metal oxide and the molecular sieve are cooperatively responsible for the aromatization of the biomass.
The biomass is various agricultural and forestry biomasses containing hemicellulose, cellulose and lignin, industrial biomass wastes and products obtained by pretreatment of the agricultural and forestry biomasses, such as 2-methylfuran, furfural, cellulose or hemicellulose.
The flue gas is a mixed gas of nitrogen (79-85.7%), carbon dioxide (7-15%) and oxygen (2.5-13%), and the main components of the biogas are methane (50-80%), carbon dioxide (20-40%) and a small amount of nitrogen (0-5%), hydrogen (< 1%), oxygen (< 0.4%), hydrogen sulfide (0.1-3%)
Preferably, the space velocity of biomass feeding is 1-8 h -1 The flow rate of the flue gas or the biogas is 60-150 ml/min.
The invention has the following beneficial effects:
1. the bimetallic catalyst has better aromatization capacity, hydrogen transfer capacity and carbon deposition resistance, mainly promotes the directional conversion and carbon dioxide reduction of biomass, and the transition metal oxide and the molecular sieve are cooperatively responsible for the aromatization of the biomass.
2. According to the invention, the bimetallic catalyst is adopted, biomass and carbon dioxide-containing flue gas or methane are subjected to co-feeding pyrolysis, three components of biomass are directionally converted, aromatic chemicals with high yield and high selectivity are prepared, the reduction of carbon dioxide in the flue gas or methane is realized, carbon monoxide is reduced, and the biomass is pyrolyzed to generate hydrogen, so that synthesis gas is obtained, the emission of carbon dioxide is reduced, the generation of carbon deposition on the catalyst is inhibited, in addition, the biochar is obtained, the resource utilization of the biomass is realized, the climate crisis of human is relieved, and the application prospect is wide.
The specific implementation mode is as follows:
the following is a further description of the invention and is not intended to be limiting.
Example 1:
0.7361 g of ammonium heptamolybdate was dissolved in 100ml of deionized water, and 10 g of HZSM-5 (SiO) was added thereto after stirring them uniformly 2 /Al 2 O 3 = 25), stirring at 60 ℃ for 16 hours, then transferring into an oven, drying at 105 ℃ for 12 hours, calcining at 600 ℃ for 5 hours to obtain Mo/HZSM-5, then adding 0.0787 g of silver nitrate solution, stirring at 60 ℃ for 16 hours, then transferring into the oven, drying at 105 ℃ for 12 hours, calcining at 600 ℃ for 5 hours, and then tabletting, crushing and screening the obtained catalyst to 40-60 meshes. Then the catalyst is placed in a fixed bed reactor, 2-methylfuran is used as biomass model material for feeding, and the mass space velocity is 1.34h -1 The carrier gas is flue gas, the gas velocity is 90ml/min, the pyrolysis temperature is 650 ℃, the pyrolysis steam is condensed at-45 ℃ through a condensing tube to obtain the aromatic hydrocarbon chemical, the yield of the aromatic hydrocarbon chemical reaches 51.72% (relative to 2-methylfuran), 2-methylfuran and carbon dioxide are completely converted, and the selectivity of carbon monoxide and hydrogen in the non-condensable gas reaches 62.35%.
Example 2:
pulverizing Eucalyptus to 80-100 mesh, and drying in oven at 60 deg.C. 2.8568 g of glucose is addedThe copper acid and 0.6031 g of molybdenum trioxide were dissolved in 200ml of deionized water, and then the mixture was continuously stirred at 100 ℃ for 1 hour, and the precursor was transferred to 10 g of HZSM-5 (SiO) 2 /Al 2 O 3 = 25), stirring at 80 ℃ for 16 hours, then transferring into an oven, drying at 105 ℃ for 12 hours, calcining at 600 ℃ for 5 hours, tabletting, crushing and screening the catalyst to 40-60 meshes; then the catalyst is placed in a fixed bed reactor, and the mass space velocity is 4h -1 The carrier gas is flue gas, the gas velocity is 90ml/min, the pyrolysis temperature is 700 ℃, pyrolysis steam is condensed at-45 ℃ through a condenser pipe to obtain aromatic chemicals such as benzene, toluene, xylene, indene, naphthalene, methylnaphthalene and the like and uncondensable pyrolysis gas, the residual solid is biochar, the yield of the aromatic-rich chemical bio-oil is 37% (relative to the biomass raw material eucalyptus), and the yield of the biochar is 42.5% (relative to the biomass raw material eucalyptus). The non-condensable gases produced by pyrolysis may be used for synthesis gas. The carbon yield of the catalyst carbon deposition is 8.2% (relative to the biomass raw material eucalyptus).
Comparative example 1:
reference example 2 is made with the exception that the catalyst is HZSM-5, which is not modified with the supported bimetallic zinc and molybdenum. Tabletting, crushing and screening the catalyst to 40-60 meshes; then the catalyst is placed in a fixed bed reactor, and the mass space velocity is 4h -1 The carrier gas is flue gas, the gas velocity is 90ml/min, the pyrolysis temperature is 700 ℃, pyrolysis steam is condensed at-45 ℃ through a condenser pipe to obtain aromatic chemicals such as benzene, toluene, xylene, indene, naphthalene, methylnaphthalene and the like and uncondensable pyrolysis gas, and the residual solid is biochar, wherein the yield of the aromatic-rich chemical bio-oil is 23% (relative to the biomass raw material eucalyptus), and the yield of the biochar is 55.2% (relative to the biomass raw material eucalyptus). The non-condensable gases produced by pyrolysis can be used for the synthesis gas.
Comparative example 2:
reference example 2 was made, except that the catalyst was zinc molybdate and no HZSM-5 was present in the catalyst. Tabletting, crushing and screening the catalyst to 40-60 meshes; then the catalyst is placed in a fixed bed reactor, and the mass space velocity is 4h -1 The carrier gas is flue gas, the gas velocity is 90ml/min, and the pyrolysis temperature is 700 DEG CAnd condensing the pyrolysis steam at-45 ℃ through a condensing tube to obtain aromatic chemicals such as benzene, toluene, xylene, indene, naphthalene, methylnaphthalene and the like and uncondensable pyrolysis gas, wherein the residual solid is biochar, the yield of the aromatic-rich chemical bio-oil is 10.5% (relative to the biomass raw material eucalyptus), and the yield of the biochar is 49.6% (relative to the biomass raw material eucalyptus). The non-condensable gases produced by pyrolysis can be used for the synthesis gas.
Comparative example 3:
reference is made to example 2, with the difference that no flue gas is fed in. Tabletting, crushing and screening the catalyst to 40-60 meshes; then the catalyst is placed in a fixed bed reactor, and the mass space velocity is 4h -1 The carrier gas is nitrogen, the gas velocity is 90ml/min, the pyrolysis temperature is 700 ℃, pyrolysis steam is condensed at-45 ℃ through a condensing tube to obtain aromatic chemicals such as benzene, toluene, xylene, indene, naphthalene, methylnaphthalene and the like and uncondensable pyrolysis gas, and residual solid is biochar, wherein the yield of the aromatic-rich chemical bio-oil is 34.9% (relative to the biomass raw material eucalyptus), and the yield of the biochar is 39.2% (relative to the biomass raw material eucalyptus). The non-condensable gases produced by pyrolysis can be used for the synthesis gas. The carbon yield of the catalyst carbon deposition is 12.7% (relative to the biomass raw material eucalyptus).
Example 2 and comparative examples 1 and 2 show that the transition metal oxide and the molecular sieve of the invention are cooperatively responsible for the oriented aromatization of biomass to prepare aromatic chemicals with high yield and high selectivity. In example 2 and comparative example 3, it can be seen that biomass and flue gas or biogas containing carbon dioxide are co-fed and rapidly pyrolyzed, so that biomass is converted into aromatic-rich chemicals in a high-value utilization manner, and carbon deposition on a catalyst is inhibited.
Example 3:
the corn cob is crushed into 60-80 meshes and then directly put into an oven to be dried at 60 ℃ for standby. 0.23 g of nickel hydroxide is dissolved in 100ml of 0.05mol/L solution of 2-hydroxyisobutyric acid, 0.36 g of molybdenum trioxide and 100ml of deionized water are added after uniform stirring, and then continuous stirring is carried out at 100 ℃ for 1 hour, and the precursor is transferred into 6 g of HY @ HZSM-5 (SiO) 2 /Al 2 O 3 = 12.3) stirring at 80 ℃ for 16 hours, followed by transferringDrying in a drying oven at 105 ℃ for 12 hours, calcining at 600 ℃ for 5 hours, tabletting, crushing and screening the catalyst to 40-60 meshes; then the catalyst is placed in a fixed bed reactor, and the mass space velocity is 4h -1 The carrier gas is flue gas, the gas velocity is 120ml/min, the pyrolysis temperature is 650 ℃, the pyrolysis steam is condensed at-45 ℃ through a condensing tube to obtain aromatic chemicals such as benzene, toluene, xylene, indene, naphthalene, methylnaphthalene and the like and non-condensable pyrolysis gas, and the residual solid is biochar. The non-condensable gases produced by pyrolysis may be used for synthesis gas. The yield of aromatic chemicals was 35.6% (relative to biomass feedstock) and the yield of biochar was 45.1% (relative to biomass feedstock). The carbon yield of catalyst carbon deposition was 8.6% (relative to biomass feedstock).
Example 4:
drying bagasse, and crushing to 20-80 meshes for later use. Dissolving 1.9386 g zinc gluconate in 100ml deionized water, stirring, adding 0.6031 g molybdenum trioxide and 100ml deionized water, stirring at 100 deg.C for 1 hr, transferring the precursor into 10 g HZSM-5 (SiO) 2 /Al 2 O 3 = 120), stirring at 80 ℃ for 16 hours, transferring into an oven, drying at 105 ℃ for 12 hours, calcining at 600 ℃ for 5 hours, tabletting, crushing and screening the catalyst to 40-60 meshes. Then the catalyst is placed in a fixed bed reactor at the airspeed of 4h -1 The carrier gas is marsh gas, and the reaction temperature is 700 ℃. Condensing the pyrolysis steam at-40 deg.C via condenser pipe to obtain aromatic-rich bio-oil, biochar and non-condensable gas, wherein the non-condensable gas mainly comprises CO and H 2 And CH 4 And can be used for synthesis gas or used as fuel for power generation. The yield of the aromatic chemicals was 34.9% (relative to the biomass feedstock) and the biochar yield was 46.2% (relative to the biomass feedstock). The carbon yield of catalyst carbon deposition was 8.4% (relative to biomass feedstock).
Example 5:
pulverizing pine wood to 20-80 mesh, and drying at 60 deg.C. 1.4722 g of ammonium heptamolybdate is dissolved in deionized water, and 10 g of HZSM-5 (SiO) is added after uniform stirring 2 /Al 2 O 3 = 38) stirring at 60 ℃ for 16 hours, followed byTransferring into an oven, drying for 12 hours at 105 ℃, calcining for 5 hours at 600 ℃ to obtain Mo/HZSM-5, adding 100ml of 0.1mol/L chloroplatinic acid solution, stirring for 16 hours at 60 ℃, transferring into the oven, drying for 12 hours at 105 ℃, calcining for 5 hours at 600 ℃, tabletting, crushing and screening the catalyst to 20-40 meshes. The crushed pine and the catalyst are placed in a circulating fluidized bed for pyrolysis, the pyrolysis atmosphere is flue gas, the pyrolysis temperature is 600 ℃, pyrolysis steam is condensed at-40 ℃ through a condensing tube to obtain aromatic-rich biological oil and biochar, the yield of aromatic-rich chemical biological oil is 35.2% (relative to a biomass raw material), the yield of biochar is 38.7% (relative to the biomass raw material), non-condensable gas generated by pyrolysis can be used for synthesis gas, and the performance of the catalyst is not obviously reduced after 40 times of circulation.
Example 6:
1.4672 g of gallium nitrate, 1.8201 g of zinc nitrate and water are mixed, and 10 g of HZSM-5@ HY (SiO) is added 2 /Al 2 O 3 = 18.6), stirring at 80 ℃ for 16 hours, then transferring to an oven, drying at 105 ℃ for 12 hours, calcining at 600 ℃ for 5 hours, tabletting, crushing and screening the catalyst to 40-60 meshes. Sanding powder and a catalyst of a furniture factory are mixed according to the proportion of 1:1, and uniformly mixing. And pyrolyzing the mixture of the sanding powder and the catalyst in a fixed bed reactor, wherein the pyrolysis atmosphere is flue gas, the pyrolysis temperature is 650 ℃, the gas velocity is 100ml/min, pyrolysis steam is condensed at-45 ℃ through a condensing tube to obtain aromatic hydrocarbon-rich bio-oil and uncondensable pyrolysis gas, and the residual solid is biochar. The non-condensable gases produced by pyrolysis can be used for the synthesis gas. The yield of aromatic chemicals was 41.8% (relative to biomass feedstock) and the yield of biochar was 37.1% (relative to biomass feedstock). The carbon yield of catalyst carbon deposition was 9.1% (relative to biomass feedstock).
Example 7:
crushing corn stalks to 20-80 meshes, and drying at 60 ℃ for later use. Zinc nitrate and aluminum nitrate were mixed as Zn/Al =1: dissolving 2 proportion in 100ml deionized water, stirring at 70 deg.C, adding ammonia water or ammonium carbonate solution, adjusting pH to 7, aging at 70 deg.C for 2 hr, filtering, washing, drying, and purifying at 500 deg.CCalcining at the temperature of 5 ℃ for 5 hours to obtain 5 g of ZnAl spinel catalyst and 5 g of HZSM-5 (SiO) 2 /Al 2 O 3 = 81) mixing molecular sieves to obtain the bimetal modified spinel and molecular sieve composite catalyst, wherein the particle size of the catalyst is 40-60 meshes. And (3) putting the crushed corn straws and the catalyst into a circulating fluidized bed for pyrolysis, wherein the pyrolysis atmosphere is methane, the pyrolysis temperature is 600 ℃, and pyrolysis steam is condensed to obtain aromatic-rich biological oil and biological carbon, wherein the yield of the aromatic-rich chemical biological oil is 55%, and the yield of the biological carbon is 22.3%. The non-condensable gas generated by pyrolysis can be used for synthesis gas, and the performance of the catalyst is not obviously reduced after 50 times of circulation.
Example 8:
dissolving 1.4520 g ferric nitrate in 100ml deionized water, stirring well, adding 5 g ceric oxide, stirring at 60 deg.C for 12h, drying at 90 deg.C for 12h, calcining at 500 deg.C for 5 h, and mixing with 5 g HY (SiO) 2 /Al 2 O 3 = 2.6) molecular sieve mechanical mixing, tabletting, crushing and screening to 40-60 meshes. Then the catalyst is placed in a fixed bed reactor, furfural is used as biomass molding material for feeding, and the mass space velocity is 2h -1 The carrier gas is marsh gas, the gas velocity is 60ml/min, the pyrolysis temperature is 650 ℃, the pyrolysis steam is condensed at minus 45 ℃ to obtain aromatic compounds, the yield of aromatic carbon reaches 49.5%, and the selectivity of carbon monoxide and hydrogen in non-condensable gas reaches 67.9%.
Example 9:
the pine is crushed to 60-80 meshes and then directly put into an oven to be dried at 60 ℃ for standby. 0.2324 g of cobalt hydroxide is dissolved in 100ml of 0.05mol/L2-hydroxyisobutyric acid solution, after uniform stirring, 0.25 g of chromium trioxide and 100ml of deionized water are added, then continuous stirring is carried out at 100 ℃ for 1 hour, and the precursor is transferred into 6 g of HZSM-5 (SiO. RTM.) (HZSM-5) solution 2 /Al 2 O 3 = 25), stirring for 16 hours at 60 ℃, then transferring into an oven, drying for 12 hours at 105 ℃, calcining for 5 hours at 600 ℃, tabletting, crushing and screening the catalyst to 40-60 meshes; then the catalyst is placed in a fixed bed reactor, and the mass space velocity is 4h -1 The carrier gas is flue gas, the gas speed is 120ml/min,the pyrolysis temperature is 650 ℃, the pyrolysis steam is condensed at-45 ℃ through a condensing tube to obtain aromatic chemicals such as benzene, toluene, xylene, indene, naphthalene, methylnaphthalene and the like and uncondensable pyrolysis gas, and the residual solid is biochar. The non-condensable gases produced by pyrolysis may be used for synthesis gas. The yield of aromatic chemicals was 42.6% (relative to biomass feedstock) and the yield of biochar was 38.1% (relative to biomass feedstock). The carbon yield of catalyst carbon deposition was 7.9% (relative to biomass feedstock).
Example 10:
crushing corn stalks to 20-80 meshes, and drying at 60 ℃ for later use. 2.4786 g of ammonium metatungstate and 1.5223 g of titanium trichloride were dissolved in 100ml of deionized water, stirred uniformly at 70 ℃ and then transferred to 10 g of HZSM-5 (SiO) 2 /Al 2 O 3 = 38), stirring at 60 ℃ for 12 hours, transferring to an oven, drying at 105 ℃ for 12 hours, calcining at 500 ℃ for 5 hours, tabletting, crushing and screening the catalyst to 40-60 meshes. And (3) putting the crushed corn straws and the catalyst into a fixed bed for pyrolysis, wherein the pyrolysis atmosphere is methane, the pyrolysis temperature is 600 ℃, pyrolysis steam is condensed at-45 ℃ through a condensing tube to obtain aromatic-rich bio-oil and biochar, and non-condensable gas generated by pyrolysis can be used for synthesis gas. The yield of aromatic chemicals was 39.6% (relative to biomass feedstock) and the biochar yield was 37.9% (relative to biomass feedstock). The carbon yield of catalyst carbon deposition was 8.7% (relative to biomass feedstock).
Example 11:
pulverizing Eucalyptus globulus into 20-80 mesh, and drying at 60 deg.C. 3.3926 g of zirconium nitrate and 0.5186 g of ruthenium trichloride are dissolved in 100ml of deionized water, stirred uniformly at 60 ℃, and then transferred into 10 g of HZSM-5 (SiO) 2 /Al 2 O 3 = 38), after stirring at 60 ℃ for 12 hours, transferring to an oven, drying at 105 ℃ for 12 hours, calcining at 450 ℃ for 5 hours, tabletting, crushing, and screening the catalyst to 40-60 meshes. Putting the crushed eucalyptus and the catalyst in a fixed bed for pyrolysis, wherein the pyrolysis atmosphere is methane, the pyrolysis temperature is 600 ℃, pyrolysis steam is condensed at-45 ℃ through a condensing tube to obtain aromatic-rich bio-oil and biochar, and uncondensable generated by pyrolysisThe gas may be used for synthesis gas. The yield of aromatic chemicals was 37.9% (relative to biomass feedstock) and the yield of biochar was 42.5% (relative to biomass feedstock). The carbon yield of catalyst carbon deposition was 7.0% (relative to biomass feedstock).
The above detailed description is specific to possible embodiments of the present invention, and the embodiments are not intended to limit the scope of the present invention, and all equivalent implementations or modifications that do not depart from the scope of the present invention should be included in the present invention.
Claims (9)
1. A method for directionally preparing aromatic hydrocarbon chemicals, synthesis gas and biochar by coupling biomass pyrolysis with carbon dioxide is characterized by comprising the following steps:
1) Preparing a bimetallic catalyst; the bimetallic catalyst is a bimetallic modified molecular sieve catalyst or a bimetallic modified spinel and molecular sieve composite catalyst, the metals are two of molybdenum, iron, gallium, zinc, nickel, copper, tungsten, cobalt, chromium, titanium, cerium, ruthenium, zirconium, aluminum, platinum or silver, the metal load accounts for 0.2-5% of the mass of the molecular sieve, the molecular sieve is any one of HZSM-5, HY @ HZSM-5 and HZSM-5@ HY, and SiO 2 /Al 2 O 3 ＝2-120；
2) Crushing and screening biomass until the particle size is less than 1cm;
3) Putting the prepared catalyst into a reactor, adding the screened biomass into the reactor, introducing flue gas or methane, pyrolyzing at 500-750 ℃, directionally converting cellulose, hemicellulose and lignin in the biomass into aromatic hydrocarbon or derivatives thereof, condensing and collecting steam generated by fast pyrolysis, wherein the condensing temperature is-45-40 ℃, the obtained liquid product is the prepared aromatic hydrocarbon chemical, and the non-condensable pyrolysis gas is rich in carbon monoxide and hydrogen and is used as synthesis gas; the solid produced is biochar.
2. The method according to claim 1, wherein the pyrolysis in step 3) is carried out at 600 to 700 ℃.
3. The method of claim 1, wherein the bimetallic catalyst is prepared by an impregnation method or a coprecipitation method, comprising the steps of:
dissolving the salt of the metal A in deionized water, adding the mixture into a molecular sieve after uniformly stirring, stirring for 8 to 16 hours at the temperature of between 40 and 80 ℃, then transferring the mixture into an oven, drying for 12 hours at the temperature of 105 ℃, calcining for 2 to 5 hours at the temperature of between 500 and 700 ℃, then adding the salt solution of the metal B, stirring for 8 to 16 hours at the temperature of between 40 and 80 ℃, then transferring the mixture into the oven, drying for 12 hours at the temperature of 105 ℃, and calcining for 2 to 5 hours at the temperature of between 450 and 700 ℃;
or dissolving the hydroxide of the metal A in 2-hydroxyisobutyric acid, adding the oxide of the metal B and water, stirring uniformly at 100 ℃, transferring into a molecular sieve, stirring for 8-16 hours at 60-80 ℃, transferring into an oven, drying for 12 hours at 105 ℃, and calcining for 2-5 hours at 450-700 ℃;
or, the salt solution of the metal A and the salt solution of the metal B or the oxide are evenly stirred at the temperature of 60-100 ℃, then are transferred into a molecular sieve, are stirred for 8-16 hours at the temperature of 40-80 ℃, are transferred into an oven, are dried for 12 hours at the temperature of 105 ℃, and are calcined for 2-5 hours at the temperature of 450-700 ℃;
or, the salt solution of the metal A and the salt solution of the metal B or the oxide are stirred uniformly at the temperature of 60-100 ℃, then are directly filtered, dried at the temperature of 90 ℃, calcined at the temperature of 450-700 ℃ and then are mechanically mixed with a molecular sieve;
or dissolving nitrates of the metals A and B in deionized water according to a proportion, adding ammonia water or ammonium carbonate solution after stirring uniformly at 65-75 ℃, adjusting the pH to 7-8, aging at 60-80 ℃ for 1-5 hours, then filtering, washing, drying, calcining at 450-1000 ℃ for 2-5 hours, and mixing with a molecular sieve to obtain the composite catalyst.
4. The method of claim 3, wherein the resulting bimetallic catalyst is further tableted, crushed, and screened to 20-80 mesh.
5. The method of claim 1, wherein the biomass is agricultural, forestry, industrial biomass waste comprising hemicellulose, cellulose, and lignin, and pre-treated products thereof.
6. The method of claim 1, wherein the biomass is 2-methylfuran, furfural, cellulose, or hemicellulose.
7. The method according to claim 1, wherein the composition of the flue gas is, in a total volume fraction of 100%: 79 to 85.7 percent of nitrogen, 7 to 15 percent of carbon dioxide and the balance of oxygen; the methane comprises 50-80% of methane, 20-40% of carbon dioxide, less than 5% of nitrogen, less than 1% of hydrogen, less than 0.4% of oxygen and 0.1-3% of hydrogen sulfide according to the total volume fraction of 100%.
8. The method of claim 1, wherein the biomass feed space velocity is 1-8 h -1 The flow rate of the flue gas or the biogas is 60-150 ml/min.
9. The method according to claim 1, wherein the aromatic hydrocarbon is one or more of benzene, toluene, xylene, indene, naphthalene, and methylnaphthalene.
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