CN117487593A - Method for preparing green chemicals by biomass fractional utilization - Google Patents
Method for preparing green chemicals by biomass fractional utilization Download PDFInfo
- Publication number
- CN117487593A CN117487593A CN202311451359.6A CN202311451359A CN117487593A CN 117487593 A CN117487593 A CN 117487593A CN 202311451359 A CN202311451359 A CN 202311451359A CN 117487593 A CN117487593 A CN 117487593A
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- CN
- China
- Prior art keywords
- biomass
- treatment
- gas
- pyrolysis
- temperature
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000002028 Biomass Substances 0.000 title claims abstract description 234
- 238000000034 method Methods 0.000 title claims abstract description 153
- 239000000126 substance Substances 0.000 title claims abstract description 55
- 239000007789 gas Substances 0.000 claims abstract description 199
- 238000011282 treatment Methods 0.000 claims abstract description 144
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 132
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 130
- 238000000197 pyrolysis Methods 0.000 claims abstract description 109
- 238000002309 gasification Methods 0.000 claims abstract description 96
- 239000003610 charcoal Substances 0.000 claims abstract description 67
- 239000002994 raw material Substances 0.000 claims abstract description 57
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 38
- 239000001301 oxygen Substances 0.000 claims abstract description 38
- 230000001105 regulatory effect Effects 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims description 121
- 230000008569 process Effects 0.000 claims description 95
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 51
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 44
- 239000011593 sulfur Substances 0.000 claims description 44
- 229910052717 sulfur Inorganic materials 0.000 claims description 43
- 229910052739 hydrogen Inorganic materials 0.000 claims description 35
- 238000000926 separation method Methods 0.000 claims description 35
- 150000001412 amines Chemical class 0.000 claims description 27
- 239000002737 fuel gas Substances 0.000 claims description 25
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 21
- 239000000463 material Substances 0.000 claims description 17
- 238000002485 combustion reaction Methods 0.000 claims description 14
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 9
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 9
- 239000011591 potassium Substances 0.000 claims description 9
- 229910052700 potassium Inorganic materials 0.000 claims description 9
- 239000011734 sodium Substances 0.000 claims description 9
- 229910052708 sodium Inorganic materials 0.000 claims description 9
- 230000002194 synthesizing effect Effects 0.000 claims description 9
- 239000004480 active ingredient Substances 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 230000009466 transformation Effects 0.000 claims description 5
- 238000006555 catalytic reaction Methods 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 13
- 239000000428 dust Substances 0.000 abstract description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 144
- 239000000047 product Substances 0.000 description 29
- 238000000746 purification Methods 0.000 description 24
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 22
- 239000003546 flue gas Substances 0.000 description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 20
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 20
- 229910052799 carbon Inorganic materials 0.000 description 20
- 239000003054 catalyst Substances 0.000 description 20
- 239000000295 fuel oil Substances 0.000 description 19
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 18
- 238000001035 drying Methods 0.000 description 17
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 16
- 238000010521 absorption reaction Methods 0.000 description 15
- 239000001257 hydrogen Substances 0.000 description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 14
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 14
- 230000009471 action Effects 0.000 description 13
- 239000003337 fertilizer Substances 0.000 description 13
- 239000006227 byproduct Substances 0.000 description 12
- 239000002253 acid Substances 0.000 description 11
- 238000011084 recovery Methods 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 10
- 238000005406 washing Methods 0.000 description 10
- 229910021529 ammonia Inorganic materials 0.000 description 9
- 239000000446 fuel Substances 0.000 description 9
- 229910002092 carbon dioxide Inorganic materials 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 8
- 239000002893 slag Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 230000005611 electricity Effects 0.000 description 7
- 239000002699 waste material Substances 0.000 description 7
- 239000001569 carbon dioxide Substances 0.000 description 6
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- 230000000996 additive effect Effects 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 238000002955 isolation Methods 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 239000003245 coal Substances 0.000 description 4
- 238000005262 decarbonization Methods 0.000 description 4
- 238000006477 desulfuration reaction Methods 0.000 description 4
- 230000023556 desulfurization Effects 0.000 description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 4
- 238000011031 large-scale manufacturing process Methods 0.000 description 4
- 230000001737 promoting effect Effects 0.000 description 4
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- 235000017166 Bambusa arundinacea Nutrition 0.000 description 3
- 235000017491 Bambusa tulda Nutrition 0.000 description 3
- 241001330002 Bambuseae Species 0.000 description 3
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 3
- 239000011425 bamboo Substances 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 235000015097 nutrients Nutrition 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 239000002689 soil Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 238000011144 upstream manufacturing Methods 0.000 description 3
- 239000002912 waste gas Substances 0.000 description 3
- 239000002023 wood Substances 0.000 description 3
- PVXVWWANJIWJOO-UHFFFAOYSA-N 1-(1,3-benzodioxol-5-yl)-N-ethylpropan-2-amine Chemical compound CCNC(C)CC1=CC=C2OCOC2=C1 PVXVWWANJIWJOO-UHFFFAOYSA-N 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- GQWWGRUJOCIUKI-UHFFFAOYSA-N 2-[3-(2-methyl-1-oxopyrrolo[1,2-a]pyrazin-3-yl)propyl]guanidine Chemical compound O=C1N(C)C(CCCN=C(N)N)=CN2C=CC=C21 GQWWGRUJOCIUKI-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- QMMZSJPSPRTHGB-UHFFFAOYSA-N MDEA Natural products CC(C)CCCCC=CCC=CC(O)=O QMMZSJPSPRTHGB-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000012824 chemical production Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 230000009849 deactivation Effects 0.000 description 2
- 235000013399 edible fruits Nutrition 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 230000008635 plant growth Effects 0.000 description 2
- 238000005057 refrigeration Methods 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 239000010902 straw Substances 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 208000005156 Dehydration Diseases 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- FFBHFFJDDLITSX-UHFFFAOYSA-N benzyl N-[2-hydroxy-4-(3-oxomorpholin-4-yl)phenyl]carbamate Chemical compound OC1=C(NC(=O)OCC2=CC=CC=C2)C=CC(=C1)N1CCOCC1=O FFBHFFJDDLITSX-UHFFFAOYSA-N 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000004720 fertilization Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 230000012010 growth Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- -1 hydrocarbon oxygen compounds Chemical class 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000003541 multi-stage reaction Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- BITYAPCSNKJESK-UHFFFAOYSA-N potassiosodium Chemical compound [Na].[K] BITYAPCSNKJESK-UHFFFAOYSA-N 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 238000001226 reprecipitation Methods 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- RAHZWNYVWXNFOC-UHFFFAOYSA-N sulfur dioxide Inorganic materials O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 239000002918 waste heat Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- 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
- C10J3/58—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels combined with pre-distillation of the fuel
- C10J3/60—Processes
- C10J3/64—Processes with decomposition of the distillation products
- C10J3/66—Processes with decomposition of the distillation products by introducing them into the gasification zone
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
- C01B3/12—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of water vapour with carbon monoxide
- C01B3/16—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of water vapour with carbon monoxide using catalysts
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
- C01B3/52—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with liquids; Regeneration of used liquids
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/02—Preparation, purification or separation of ammonia
- C01C1/04—Preparation of ammonia by synthesis in the gas phase
- C01C1/0405—Preparation of ammonia by synthesis in the gas phase from N2 and H2 in presence of a catalyst
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
- C07C1/04—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
- C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
- C07C29/1516—Multisteps
- C07C29/1518—Multisteps one step being the formation of initial mixture of carbon oxides and hydrogen for synthesis
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
- C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
-
- 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
- C10J3/72—Other features
- C10J3/80—Other features with arrangements for preheating the blast or the water vapour
-
- 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
- C10J3/72—Other features
- C10J3/82—Gas withdrawal means
- C10J3/84—Gas withdrawal means with means for removing dust or tar from the gas
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K1/00—Purifying combustible gases containing carbon monoxide
- C10K1/002—Removal of contaminants
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K1/00—Purifying combustible gases containing carbon monoxide
- C10K1/002—Removal of contaminants
- C10K1/003—Removal of contaminants of acid contaminants, e.g. acid gas removal
- C10K1/004—Sulfur containing contaminants, e.g. hydrogen sulfide
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K1/00—Purifying combustible gases containing carbon monoxide
- C10K1/002—Removal of contaminants
- C10K1/003—Removal of contaminants of acid contaminants, e.g. acid gas removal
- C10K1/005—Carbon dioxide
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K1/00—Purifying combustible gases containing carbon monoxide
- C10K1/08—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors
- C10K1/10—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors with aqueous liquids
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K3/00—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide
- C10K3/02—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide by catalytic treatment
- C10K3/04—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide by catalytic treatment reducing the carbon monoxide content, e.g. water-gas shift [WGS]
-
- 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
- C10J2300/0913—Carbonaceous raw material
- C10J2300/0916—Biomass
- C10J2300/092—Wood, cellulose
-
- 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
- C10J2300/0959—Oxygen
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- 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
- C10J2300/16—Integration of gasification processes with another plant or parts within the plant
- C10J2300/1603—Integration of gasification processes with another plant or parts within the plant with gas treatment
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- 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
- C10J2300/16—Integration of gasification processes with another plant or parts within the plant
- C10J2300/1603—Integration of gasification processes with another plant or parts within the plant with gas treatment
- C10J2300/1615—Stripping
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- 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
- C10J2300/16—Integration of gasification processes with another plant or parts within the plant
- C10J2300/1603—Integration of gasification processes with another plant or parts within the plant with gas treatment
- C10J2300/1618—Modification of synthesis gas composition, e.g. to meet some criteria
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- 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
- C10J2300/16—Integration of gasification processes with another plant or parts within the plant
- C10J2300/1687—Integration of gasification processes with another plant or parts within the plant with steam generation
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- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
Abstract
The invention discloses a method for preparing green chemicals by biomass split utilization, which comprises the steps of carrying out pyrolysis treatment on biomass raw materials; gasifying biomass charcoal and oxygen which are pyrolysis products to prepare synthesis gas; and (3) regulating the gas composition ratio of the gasified synthetic gas, and then carrying out synthesis treatment to obtain the green chemical. The method solves the problems that biomass gasification equipment in the existing biomass gasification production of green chemicals cannot be high-pressure and large-sized, tar and dust in synthetic gas are difficult to treat, the operation period is short and the like, and meets the requirements of continuous, stable and efficient production of green chemicals by carrying out biomass pyrolysis and gasifying biomass charcoal which is a pyrolysis product step by step.
Description
Technical Field
The invention relates to a green chemical production process, in particular to a green chemical production process based on biomass quality-dividing utilization, and belongs to the technical field of biomass pyrolysis coupling chemical industry.
Background
The existing biomass green chemical preparation process routes mostly adopt a biomass direct gasification mode, generally adopt gasification technologies such as a fixed bed and a fluidized bed, have the problems that the active ingredients in the synthetic gas are low, the tar and dust content in the gas is high, the treatment is difficult, the gasification equipment cannot be subjected to high-pressure large-scale production, and the like, and are always difficult to utilize biomass in a high-value way.
The biomass raw material has the characteristics of high volatile matter, low carbon fixation, low ash content and the like, is more suitable for a step-by-step gasification process of pyrolysis and gasification, light components such as fuel gas, tar and the like after pyrolysis are sent to a boiler to be combusted to generate high-pressure steam as driving steam of large-scale compressor equipment, biomass charcoal heat value after pyrolysis and quality improvement is higher (4500 kCal/kg or more), the biomass charcoal heat value is sent to a high-pressure dry powder entrained flow gasifier to be gasified efficiently, and green chemicals are prepared by using the generated crude synthetic gas, so that the biomass raw material is a process route with higher reliability and feasibility of large-scale production.
The dry powder pressurized entrained-flow gasification technology is a clean and high-efficiency technology for converting various carbon-containing solid raw materials into main materials under the high-temperature and high-pressure environmentThe basic principle of advanced technology is to grind carbon-containing material into dry powder with proper granularity by using high-temperature inert gas (CO) 2 /N 2 ) Continuously feeding into an entrained flow gasifier, supplementing oxygen, and reacting under high temperature and high pressure to generate crude gas hydrogen and carbon monoxide. The dry powder pressurized entrained flow gasification technology is a gasification technology with high reliability, and according to domestic experience, the continuous operation days of a single set of device of the gasification technology can reach more than 300 days.
The biomass gasification equipment successfully solves the problems that the existing biomass gasification equipment cannot be large-sized under high pressure, the synthetic gas contains tar and dust which are difficult to treat, equipment and pipelines are easy to be blocked, and the shutdown and the short operation period are frequently caused.
Disclosure of Invention
In order to solve the problems that biomass gasification equipment in the existing biomass gasification production of green chemicals cannot be high-pressure and large-sized, tar and dust in synthetic gas are difficult to treat, the operation period is short and the like, the invention provides a process for producing green chemicals based on biomass step-by-step pyrolysis and gasification.
In order to achieve the aim of the invention, one aspect of the invention provides a method for preparing green chemicals by biomass split utilization, which comprises the steps of carrying out pyrolysis treatment on biomass raw materials; gasifying biomass charcoal and oxygen which are pyrolysis products to prepare synthesis gas; and (3) regulating the gas composition ratio of the gasified synthetic gas, and then carrying out synthesis treatment to obtain the green chemical.
Wherein the pyrolysis treatment is low-temperature pyrolysis, wherein the pyrolysis treatment temperature is less than or equal to 500 ℃, and preferably 350-500 ℃.
In particular, the gasification treatment temperature is 900-1000 ℃; the relative pressure is 3.5-6.5 MPa.
In particular, the green chemical is methanol, ethanol, ammonia, methane, fuel oil or ethylene glycol, preferably methanol, fuel oil.
In particular, the method also comprises the steps of carrying out conversion treatment on the synthesis gas generated by gasification treatment, adjusting the composition ratio of the gas and then carrying out the synthesis treatment.
In another aspect, the present invention provides a method for preparing green chemicals by fractional utilization of biomass, comprising the steps of:
1) Pretreatment of
Pretreating a biomass raw material to obtain a pretreated biomass material with a water content of less than 15% and a particle size of less than 5 cm;
2) Pyrolysis treatment
Carrying out pyrolysis treatment on the pretreated biomass material, and carrying out pyrolysis to generate biomass fuel gas, biomass tar and biomass charcoal;
3) Preparation of high-temperature high-pressure steam
The biomass fuel gas and the biomass tar are sent into a steam boiler to be subjected to boiler treatment, namely the biomass fuel gas and the biomass tar are combusted in the boiler to provide heat, and water in the boiler is heated to prepare high-temperature and high-pressure water vapor;
4) Space division treatment
The high-temperature high-pressure water vapor prepared by the boiler is used as driving vapor of a compressor to perform air separation treatment (namely air separation treatment) to obtain high-pressure oxygen for later use;
5) Gasification treatment
Gasifying high-pressure oxygen prepared by biomass charcoal and air separation under high-temperature and high-pressure conditions, wherein the biomass charcoal, oxygen and water react to prepare crude synthesis gas and ash containing sodium and potassium, and the active ingredients in the crude synthesis gas are CO and H 2 ；
6) Transformation process
The conversion treatment is carried out on the crude synthesis gas, and CO and H in the crude synthesis gas are regulated 2 To obtain a conversion synthesis gas;
7) Purifying treatment
Purifying the shift synthesis gas to remove sulfur and CO in the shift synthesis gas 2 To obtainClean syngas, such that the clean syngas contains only CO and H 2 ；
8) Synthesis treatment
Synthesizing the clean synthesis gas under high pressure and catalysis conditions, and carrying out CO and H 2 Chemical reaction occurs to synthesize green chemicals.
Wherein, the pretreatment in the step 1) comprises: firstly, crushing a biomass raw material to prepare a crushed material with the particle size smaller than 5 cm; and then drying the crushed material to obtain the pretreated biomass material with the water content lower than 15%.
In particular, the particle diameter of the crushed material is preferably 1 to 3cm; the water content of the pretreated biomass material is preferably 0-10%.
In particular, the temperature of the drying treatment is 100-200 ℃.
And (3) placing the crushed materials in a baking oven, introducing high-temperature boiler flue gas as a drying medium, drying the crushed materials, and dehydrating until the water content is lower than 15%.
In particular, the biomass feedstock includes agricultural and forestry waste.
In particular, the agricultural and forestry waste is selected from various agricultural and forestry waste such as crop straws, bamboo scraps, wood chips, wood scraps, fallen leaves and fruit tree branches.
In particular, the biomass feedstock is an internationally recognized biomass material that can be used as a renewable energy source.
Wherein the temperature of the pyrolysis treatment in step 2) is less than or equal to 500 ℃, preferably 350-500 ℃, and more preferably 400+/-5 ℃; the pyrolysis treatment time is 10-30min, preferably 20min.
In particular, the pyrolysis treatment is an oxygen barrier pyrolysis treatment performed under micropressure conditions.
In particular, the micropressure condition is that the relative pressure in the pyrolysis furnace is 0.5-1kPa.
In the pyrolysis process, the relative pressure in the pyrolysis furnace is controlled to be 0.5-1kPa, so that the pyrolysis furnace is in a micro-positive pressure state, and the pyrolysis treatment is ensured to be oxygen-isolation high-temperature heat treatment.
In particular, the volatile content of the biomass charcoal of the pyrolysis product is less than or equal to 30 percent, preferably 10 to 30 percent.
An efficient advanced oxygen-isolation continuous indirect heating type medium-temperature pyrolysis device is adopted, and the pyrolysis temperature is less than or equal to 500 ℃.
Because the biomass gas and the biomass tar which are pyrolysis products contain a certain amount of dust impurities and have complex components, a complex separation and purification system is needed for directly taking the biomass gas and the biomass tar as raw materials, and the investment and the consumption are relatively high, the biomass gas and the biomass tar are directly sent into a steam boiler by adopting a boiler treatment method, and the biomass gas and the biomass tar are burnt in the boiler to provide heat, heat water in the boiler is heated, and high-temperature and high-pressure water vapor is prepared for providing driving steam in a process system;
in particular, the high temperature and high pressure steam produced in step 3) has a temperature of 500-540 ℃ (preferably 540 ℃); the relative pressure is 9-10MPa (preferably 9.8 MPa).
In the process of preparing high-temperature high-pressure water vapor (also called as 'boiler' treatment), high-temperature boiler flue gas generated by burning biomass fuel gas and biomass tar is used as a drying medium for pretreatment of biomass raw materials, the biomass raw materials are dried in an indirect heat exchange mode, and the dried low-temperature boiler flue gas is recycled to the boiler for treatment and then is discharged.
In particular, the high-pressure boiler is used for carrying out the boiler treatment by adopting a high-efficiency high-pressure gas boiler with a fuel nozzle, high-temperature high-pressure water vapor is prepared, and the generated vapor pressure parameter is 9.8MPa (g) and 540 ℃.
CO generated by combustion of biomass fuel gas and biomass tar in boiler treatment process 2 Absorbing by organic amine solution absorption method, collecting and storing.
In particular, the relative pressure of the high-pressure oxygen in step 4) is between 5.0 and 7.5MPa.
In particular, the gasification treatment in step 5) is carried out at a temperature of 900-1000 ℃; the relative pressure is 3.5-6.5MPa.
In particular, the ratio of the mass of biomass charcoal to the volume of oxygen in the standard state is (167-200): 100 (kg/m) 3 ) Preferably 200:100 (kg/m) 3 ) The method comprises the steps of carrying out a first treatment on the surface of the Air flowThe chemical treatment temperature is 900-1000 ℃, preferably 950 ℃; the pressure of gasification treatment is 3.5-6.5MPa, preferably 6.0MPa; the treatment time is 8 to 12s, preferably 10s.
In particular, the gasification treatment is carried out by adopting a high-pressure pulverized coal entrained-flow bed, wherein the relative pressure in the gasification treatment process is controlled to be 3.5-6.5MPa.
In the invention, the gasification reaction temperature is reduced, and when the conventional carbon-containing raw materials are gasified (such as coal), the gasification reaction temperature is generally higher than the melting point (flow temperature FT) of raw material ash by more than 100 ℃, so that the raw material reaction is ensured to be sufficient, and ash in the raw material can be sufficiently melted for treatment; however, for biomass charcoal raw materials, ash in biomass charcoal is mainly oxides containing sodium and potassium, and the substances are all low-melting-point oxides.
In particular, step 6) uses a wide temperature range sulfur tolerant shift catalyst to perform the shift treatment on the raw syngas to regulate CO and H in the raw syngas 2 To obtain a conversion synthesis gas;
wherein CO and H in the synthesis gas are converted 2 According to the volume ratio of the green chemical to be prepared, the corresponding H is adjusted 2 And the volume ratio of CO.
In the synthetic gas conversion treatment process, according to different green chemicals, a wide-temperature sulfur-resistant conversion catalyst corresponding to the green chemicals which is known in the prior art is adopted to carry out corresponding conversion treatment, and CO and H in the synthetic gas are regulated 2 To the volume ratio of CO and H required for synthesizing the corresponding green chemical 2 Is matched with the volume ratio of the (a).
In particular, the shift treatment is performed using an isothermal shift converter.
Isothermal conversion is an improved process for traditional adiabatic conversion, and the isothermal conversion furnace replaces heat pipes in the catalyst bed to maintain the temperature balance of the bed by timely removing heat generated by the reaction. In the isothermal conversion process, the reaction heat is directly taken away by the steam generated by the steam drum connected with the conversion furnace, so that the conversion reaction temperature is reduced. Compared with the traditional adiabatic conversion process, the isothermal conversion can effectively control the reaction temperature of the conversion furnace to be carried out at a proper temperature; the method effectively ensures wider adaptability to temperature in the conversion reaction process, mild reaction, reduces the number of required conversion sections, reduces the resistance drop of the synthesis gas, and is a safe, reliable and energy-saving conversion process.
The synthesis gas generally contains CO 2 、CH 4 、N 2 And sulfide and other impurity components, and the effective component has high CO content, and the aim of transformation is to react CO in the crude synthesis gas with water vapor to generate CO 2 And H 2 。
The shift reaction is a reversible exothermic reaction, the reaction is more intense under the action of the catalyst, and simultaneously, a large amount of heat is released, and the equilibrium conversion rate is continuously reduced along with the increase of the temperature. The CO content in the raw gas can generally reach more than 60%, the heat insulation temperature rise of the shift reaction is larger due to higher CO content, in order to obtain higher conversion rate, the CO content index of a shift outlet is ensured to be lower (for example, the CO content of raw gas required by synthesizing methanol needs to be reduced to about 33 percent), and the reaction heat is required to be continuously removed, so the shift reaction is generally carried out in multiple stages, and the core equipment is a shift converter and a heat exchanger; because the shift reaction is a catalytic reaction, a sulfur-tolerant catalyst is selected to solve the problem of catalyst deactivation in a sulfur environment.
The synthesis gas from the gasification treatment is fed in sequence to one or more shift stages (raw materials (H) according to conventional synthesis methods for downstream synthesis of the desired product 2 And CO), each section of conversion procedure consists of a conversion furnace, a heat exchanger, a waste pot and other equipment, and the heat exchanger and the waste pot remove heat generated by the conversion reaction through the type of byproduct steam, thereby being beneficial to the next section of conversion reaction.
The reaction temperature of the first-stage shift converter for shift treatment is generally controlled to be 180-350 ℃, which is lower than that of the conventional first-stage shift converter (generally above 450 ℃), and the operating pressure is generally slightly lower than that of the raw synthesis gas sent by gasification. The synthesis gas is obtained after passing through the conversion section and is suitable for the purpose of downstream synthesisH of the product 2 And CO ratio, e.g., H2 and CO ratio of about 2.05 required for methanol synthesis: 1.
in particular, the low-temperature methanol washing process method is adopted in the step 7) to carry out the purification treatment on the shift conversion synthesis gas, so as to remove sulfur and CO in the shift conversion synthesis gas 2 Wherein cold methanol (-55 ℃ to minus 35 ℃) is used as an absorption solvent, and the characteristic of extremely high solubility of the methanol to the acid gas at low temperature is utilized to remove the acid gas in the raw material gas.
Purification of CO in synthesis gas 2 Less than 20ppm of H 2 The S content is less than 0.1ppm.
The desulfurization and decarbonization of the gas in the shifted synthesis gas may be performed in stages in the same column or in different columns, optionally.
In particular, the green chemicals described in step 8) are methanol, ethanol, ammonia, methane, fuel oil, ethylene glycol, etc.
In particular, the method also comprises the step of absorbing CO which is generated by burning the biomass fuel gas and the biomass tar in the boiler treatment process and is absorbed by the organic amine solution 2 The method comprises the steps of carrying out a first treatment on the surface of the CO absorbed by organic amine solution removed during clean-up treatment of shifted synthesis gas 2 And H 2 And (3) reacting to synthesize the green chemical.
In another aspect, a process for the production of green chemicals based on biomass split utilization is provided, comprising biomass pretreatment, biomass pyrolysis, boilers, air separation (air separation), gasification, syngas conversion, purification, sulfur recovery, synthesis, CO 2 Trapping, storing and CO 2 Synthesizing and other steps;
crushing, drying and dehydrating biomass raw materials sent from the outside through the biomass pretreatment process, taking high-temperature boiler flue gas generated by the combustion of a subsequent boiler process as a drying medium, drying (drying and dehydrating) the biomass raw materials in an indirect heat exchange mode, and recycling and refluxing the dried low-temperature boiler flue gas to the boiler process for treatment and then discharging; in the pyrolysis process, the pyrolysis furnace is kept to be operated by micro-positive pressure oxygen isolation, and the relative pressure in the pyrolysis furnace is 0.5-1kPa.
The operation process is that pretreated biomass raw materials (the water content is less than 15 percent, the granularity is less than 5 cm) are sent into pyrolysis equipment through feeding equipment (generally screw) for pyrolysis reaction, the mixture of biomass fuel gas and biomass fuel oil after the reaction (the fuel oil is in a gaseous state at the operation temperature) is sent into a cooling-tar separation device in a pyrolysis system, and the mixture is sent to a boiler for combustion after oil-gas separation; and cooling biomass charcoal generated by the pyrolysis reaction and then sending the cooled biomass charcoal out of the system.
The biomass pyrolysis process can adjust pyrolysis temperature and residence time according to different biomass raw material characteristics, and the heat of the pyrolysis process is generated by burning generated biomass tar and self-heating.
The biomass gas and biomass tar which are pyrolysis products are sent into a steam boiler, and the biomass gas and biomass tar are combusted in the boiler to provide heat, so that water in the boiler is heated, and high-temperature and high-pressure water vapor is produced;
the boiler treatment is to fully burn biomass fuel gas and biomass fuel oil under the action of excessive air, and the generated heat is used for generating high-pressure steam. The oil and the gas become CO after being burnt 2 、H 2 O、N 2 Flue gas evacuation of NOx.
The heat generated by the combustion of the biomass gas and the biomass tar in the boiler heats the boiler flue gas, the temperature of the boiler flue gas is increased, high-temperature boiler flue gas is formed and is used for drying and dewatering biomass raw materials, the boiler flue gas after drying the biomass flows back into the boiler and is heated again, high-temperature boiler flue gas is formed, heat energy is recycled, and the biomass raw materials are fully utilized;
the biomass fuel gas and biomass tar which are pyrolysis products are sent into a high-pressure gas boiler with a fuel nozzle for combustion treatment; CO produced by combustion of biomass fuel gas and biomass tar 2 After being discharged from the boiler, the waste water is introduced into organic amine solution to absorb CO 2 Capturing and storing CO 2 。
The biomass gas and biomass tar which are pyrolysis products are sent into a high-pressure gas boiler with an efficient fuel nozzle, the biomass gas and biomass tar are burnt in the boiler to provide heat, water in the boiler is heated to prepare high-temperature high-pressure water vapor, and the high-pressure water is heated to obtain the high-pressure water vaporThe pressure of the steam is 9.8MPa (usually 9-10 MPa); the temperature of the high pressure steam is 540 ℃ (typically 500-540 ℃); CO produced by combustion of biomass fuel gas and biomass tar 2 Discharging the gas from the high-pressure gas boiler, and collecting and storing the gas by using an organic amine solution for later use;
the high-pressure steam enters an air separation procedure to be used as driving steam of a large-sized compressor in the procedure; and (3) performing air separation treatment (namely air separation treatment) by using high-pressure steam obtained by boiler treatment to obtain high-pressure oxygen. High-pressure oxygen generated by air separation is sent into a gasification furnace and biomass charcoal to participate in the reaction together. The purity of the high-pressure oxygen is more than or equal to 99.5%; the relative pressure of the high-pressure oxygen is 5.0-7.5MPa. The gasification treatment temperature is 900-1000 ℃; the relative pressure is 3.5-6.5 MPa; the treatment time is 8-12s. The ratio of the mass of the biomass charcoal to the volume of oxygen in a standard state is (167-200): 100 (kg/m) 3 ) Preferably 200:100 (kg/m) 3 )。
H is regulated according to the difference of downstream synthetic products in the synthetic gas conversion treatment process 2 And the ratio of the volumes of CO.
Feeding the crude synthesis gas into a shift converter of a synthesis gas shift process, carrying out synthesis gas shift treatment by adopting a wide-temperature sulfur-tolerant isothermal shift process, and regulating H in the crude synthesis gas 2 And CO to make a shifted syngas, wherein H in the shifted syngas 2 And the volume ratio of CO is (1.5-.) infinity): 1, (e.g., methanol is 2.05:1; ammonia is all converted to H) 2 )。
Purifying the shift synthesis gas to remove sulfur and CO in the shift synthesis gas 2 Producing a net synthesis gas such that the net synthesis gas contains only H 2 And/or CO; sending the obtained conversion synthesis gas into a reaction tower for purification treatment to obtain clean synthesis gas; wherein the cleaning treatment removes sulfur (sulfur-containing gas) and CO from the shifted synthesis gas 2 So that the net synthesis gas contains only H 2 And/or CO, H 2 The CO ratio is the same as that of the upstream conversion process; CO removed by the purification treatment 2 Absorbing, capturing and storing the mixture by using an organic amine solution for standby; sulfur recovery treatment (sulfur recovery by claus process) of sulfur-containing gas can be used to produce sulfur productEtc
The clean synthesis gas is synthesized under high pressure under the action of a catalyst, and CO and H are treated 2 Chemical reaction is carried out to synthesize green chemicals (methanol, ethanol, ammonia, methane, fuel oil, glycol, etc.).
CO discharged from the boiler process and the purification process 2 Through the CO 2 Collecting and storing the green hydrogen as raw material after collecting, and passing the green hydrogen through the CO 2 The synthesis process finally generates green chemicals such as green methanol, fuel oil and the like; sulfur-containing gas removed in the purification process generates a sulfur byproduct through a sulfur recovery process; part of biomass charcoal generated in the biomass pyrolysis process can selectively generate charcoal base fertilizer byproducts; ash slag rich in sodium and potassium elements generated in the gasification process is also used as an additive of the compound fertilizer and is one of byproducts.
Preferably, the biomass pyrolysis process adopts a high-efficiency advanced oxygen-isolation continuous indirect heating type medium-temperature pyrolysis device, the pyrolysis temperature is less than or equal to 500 ℃, and the pyrolysis residence time is 10-30 min; the pyrolysis temperature and the residence time can be adjusted according to different biomass raw material characteristics in the biomass pyrolysis process, and the heat of the pyrolysis process is generated by burning generated biomass tar and self-heating. The biomass charcoal produced by low-temperature pyrolysis keeps a certain volatile component proportion, is beneficial to promoting the reaction activity in the gasification process and reducing the reaction temperature.
Preferably, in the air separation step, a large compressor unit for providing compression work is driven by a steam turbine and uses high-temperature and high-pressure steam generated by a boiler as driving power;
preferably, the purification process adopts an advanced low-temperature methanol washing process;
preferably, the synthesis process uses purified synthesis gas to produce chemicals such as methanol, ethanol, ammonia, methane, fuel oil, ethylene glycol, etc. under the action of a catalyst.
Preferably, said CO 2 And a synthesis procedure, namely synthesizing chemicals such as methanol, fuel oil and the like by utilizing green hydrogen and CO2 under the action of a catalyst.
Preferably, the green hydrogen is green hydrogen produced by using renewable energy sources such as wind, light, water and the like to generate electricity and passing through the electrolytic tank device.
Preferably, the sulfur recovery process employs a claus process.
The production process of green chemicals based on biomass quality utilization comprises the steps of crushing biomass raw materials such as agricultural and forestry wastes including various straws, wood chips, fallen leaves, fruit tree branches and the like, household garbage and the like through a biomass pretreatment process, drying, performing an oxygen-isolation pyrolysis reaction through a biomass pyrolysis process, and enabling pyrolyzed gas and liquid-phase products such as biomass fuel gas and biomass tar to enter a boiler process as boiler fuel for combustion, wherein pyrolyzed solid-phase product biomass charcoal enters a gasification process as main gasification raw materials for gasification reaction; the pyrolysis and gasification processes belong to two reactors, namely a stepwise reaction, and belong to two reaction stages.
The high-pressure steam generated in the boiler process is used as driving steam of a large-scale compressor unit in the air separation process, so that the air separation process can process air from natural environment, and high-pressure oxygen (5.0-7.5 MPa (g)) is generated as one of raw materials in the gasification process. CO generated in boiler process 2 Through CO 2 The collecting and storing step is used as raw material gas after collecting.
The CO and H in the crude synthesis gas generated in the gasification process are regulated by the synthesis gas conversion process 2 The ratio is adapted to chemical products such as synthetic methanol, fuel oil and the like; the crude synthesis gas sent out in the synthesis gas conversion process enters the purification process to remove sulfur and carbon dioxide, and the removed carbon dioxide enters CO 2 Collecting and storing the sulfur-containing gas as the feed gas after collecting in the collecting and storing step, and introducing the removed sulfur-containing gas into a sulfur recovery step to generate a sulfur byproduct; the purified gas sent from the purification process enters the synthesis process to finally synthesize chemicals such as methanol, fuel oil and the like.
The operation temperature of the gasification process is 900-1000 ℃, and ash slag containing sodium and potassium generated in the gasification process can be used as an additive of a compound fertilizer and is one of byproducts.
CO 2 Capturing and storing CO captured in the process 2 The raw material gas and the green hydrogen gas sent from the outside pass through CO 2 Final synthesis of synthetic procedureAnd forming methanol, fuel oil and other chemicals.
According to the production process of the green chemicals based on biomass split utilization, disclosed by the invention, the biomass pyrolysis and biomass charcoal gasification are split utilized through step-by-step reaction, so that the high-pressure, large-scale and continuous production of biomass-based chemical products is realized, the coupling of carbon dioxide trapping and storage and carbon dioxide raw material utilization is realized, and the carbon fixation effect and the product scale are improved; the invention is suitable for newly-built gasification devices and is also suitable for reconstruction by using the existing gasification devices, and can successfully realize the green transformation of the existing engineering.
Compared with the prior art, the method has the following advantages and benefits:
1. biomass low-temperature pyrolysis products are utilized in a quality-dividing manner, wherein biomass fuel gas and tar products which are difficult to process and separate are prepared into high-pressure steam and boiler flue gas through burning in a boiler, and biomass fuelling is realized by utilizing waste heat; the biomass charcoal containing a certain volatile matter enters the gasification device to react to prepare the synthetic gas, so that the raw material application of the synthetic gas is realized, and the utilization degree and efficiency of biomass are greatly improved.
2. The biomass charcoal prepared by adopting low-temperature pyrolysis treatment has certain volatile matters, the biomass charcoal containing the volatile matters is used as gasification reaction raw materials, the low-melting ash content of the biomass charcoal can obviously reduce the operation temperature of a gasification reaction gasification furnace, the energy consumption of gasification reaction is reduced, and compared with the gasification furnace taking coal as raw materials, the energy is saved;
3. The ash slag generated by the gasification furnace can be used as an additive of the compound fertilizer, so that the high-value recycling of wastes is realized;
4. in the method, the gasification reaction is carried out by taking the biomass carbon containing a certain volatile component by low-temperature pyrolysis as a raw material, so that the temperature of the gasification reaction is reduced, the gasification reaction in the gasification furnace can be operated under medium-high pressure conditions, and the large-scale production is facilitated;
5. in the whole production flow of green chemical synthesis, biomass is used as a raw material and power fuel, and the produced chemicals have green properties, so that energy sources are saved, energy consumption is reduced, and resources are recycled;
6. the method also treats greenhouse gas CO generated by boiler treatment and gasification treatment 2 The trapping and storage are realized through the organic amine solution, chemicals are prepared by combining green hydrogen, and the low carbon of the whole production process is realized.
Drawings
FIG. 1 is a schematic flow chart of a method for preparing green chemicals by biomass split utilization according to the invention.
Detailed Description
Specific embodiments of the present invention will be described in detail below with reference to the accompanying drawings.
As shown in FIG. 1, the method for preparing green chemicals by biomass split utilization comprises biomass pretreatment 1, biomass pyrolysis 2, a boiler 9, air separation 7, gasification 3, synthesis gas conversion 4, purification 5, sulfur recovery 8, synthesis 6 and CO 2 Trapping and storing 10, CO 2 Synthesizing 11 and other steps; the biomass raw material sent from the outside is crushed, dried and dehydrated in the biomass pretreatment process 1, and then enters the biomass pyrolysis process 2 to be decomposed into three products of biomass fuel gas, biomass tar and biomass charcoal; part of biomass charcoal generated in the biomass pyrolysis process 2 can selectively generate charcoal base fertilizer byproducts to play a role in carbon fixation;
the carbon-based fertilizer is an ecological environment-friendly fertilizer prepared by taking biomass carbon as a matrix and adding organic matters or/and inorganic matters according to the characteristics of different areas, different crop growth characteristics and scientific fertilization principles; the action of the carbon-based fertilizer is mainly derived from the action of biomass charcoal, which includes but is not limited to: maintaining soil moisture, increasing microbial activity, locking nutrients in soil, promoting plant growth, establishing lasting fertilizer effect, etc. The biological carbon and the organic nutrient, the inorganic nutrient and the beneficial microorganism are combined together to form the carbon-based fertilizer, so that the effects of improving soil, promoting plant growth and the like are achieved together.
The biomass fuel gas and biomass tar enter a boiler process 9 for combustion, and the heat thereof is used for heating cold water to generate high pressure Steam (general pressure 9-10 MPa, temperature 500-540 ℃). The high-pressure steam enters a subsequent air separation treatment (namely an air separation step 7) and is used as driving steam of a large-sized compressor in the air separation step; biomass charcoal as raw material and high-pressure oxygen produced in the air separation step 7 enter the gasification step 3 (gasification treatment) together, and undergo complex oxidation-reduction reaction to generate crude synthesis gas (the active ingredients are CO and H) 2 ) And ash containing sodium and potassium; the ash slag containing sodium and potassium generated in the gasification process 3 is used as an additive of the compound fertilizer and is also one of byproducts.
The operation temperature of the gasification furnace is 900-1000 ℃; the relative pressure is 3.5-6.5 MPa; the biomass charcoal and oxygen sent from the upstream are sprayed into the furnace body through a nozzle (burner) of the gasification furnace to rapidly perform high-temperature high-pressure oxidation-reduction reaction, a spray chilling device and a chilled water level are arranged at the lower part of the gasification furnace, slag in the synthesis gas is cooled mainly through a water bath method, and part of chilled water is also involved in the reaction process; the synthesis gas (the main components are CO, H2, CO2, H2O and dust) after water bath is sent out of the gasification furnace, is washed by a venturi scrubber and a washing tower in the gasification process, and is sent to the downstream conversion process after further dust removal.
The raw synthesis gas is passed through said (i.e. synthesis gas shift process 4) to regulate CO and H 2 Is subjected to the purification process 5 to remove sulfur and CO in the converted synthesis gas 2 Forming clean synthesis gas;
the purification treatment adopts a low-temperature methanol washing process: the low-temperature methanol washing process is suitable for treating CO in gas 2 And sulfide removal, wherein the process is a typical physical absorption method, and takes cold methanol (-55 ℃ to minus 35 ℃) as an absorption solvent, and utilizes the characteristic of extremely high solubility of the methanol to acid gas at low temperature to remove the acid gas in the raw gas. The process gas has high purification degree, and can change CO in the outlet synthesis gas 2 Is taken off to less than 20ppm, H 2 S is less than 0.1ppm, and the desulfurization and decarbonization of the gas can be performed in stages in the same column or in different columns selectively.
The sulfur removed in the purification step 5 is sulfur-containing gas, and the sulfur-containing gas is subjected to sulfur recovery treatment (namely, a sulfur recovery step 8) to generate a sulfur byproduct;
the purified synthesis gas is sent into a synthesis reactor for synthesis treatment (namely a synthesis process 6), and green chemicals such as methanol, ethanol, ammonia, methane, fuel oil or glycol and the like are finally generated under the action of a catalyst. CO discharged from the boiler step 9 and the purification step 5 2 Through the CO 2 The collecting and storing step 10 is carried out to collect green hydrogen which is taken as a raw material and is input from the outside and passes through the CO 2 The synthesis step 11 finally produces green chemicals such as green methanol and fuel oil.
Methods for preparing green chemicals (methanol, ethanol, ammonia, methane, fuel oil or ethylene glycol) by synthetic treatments are conventional synthetic methods existing and known in the art.
Example 1:
1. pretreatment of biomass feedstock
Crushing biomass raw materials (bamboo scraps) by using crusher equipment to prepare biomass crushed materials with the length of less than 5cm (usually 1-3 cm); then sending into a dryer for drying treatment (namely drying and dehydration treatment) to obtain pretreated biomass material with the water content of 7 percent (usually lower than 15 percent and preferably 0 to 10 percent) for standby;
in the drying treatment process, the high-temperature boiler flue gas is adopted to heat the dryer, the dried low-temperature boiler flue gas flows back into the steam boiler and is heated again to be heated into high-temperature boiler flue gas for recycling.
2. Pyrolysis treatment
The pretreated biomass material is sent into a pyrolysis furnace (a high-efficiency advanced oxygen-isolated continuous indirect heating type medium-temperature pyrolysis device), and is heated to raise the temperature for pyrolysis treatment to prepare biomass fuel gas, biomass tar and biomass charcoal;
Wherein the pyrolysis treatment temperature is controlled to 400 ℃ (usually less than or equal to 500 ℃, preferably 350-500 ℃), and the pyrolysis treatment is carried out for 20min (usually 10-30 min); maintaining the pressure in the high-temperature pyrolysis furnace at micro positive pressure, wherein the relative pressure in the pyrolysis furnace is 0.7kPa (usually 0.5-1) kPa; micro-positive pressure is generated in the pyrolysis furnace, so that oxygen is isolated in the pyrolysis process of biomass raw materials.
According to the invention, pyrolysis treatment is performed at a lower temperature, and on one hand, the pyrolysis temperature and the residence time of the biomass pyrolysis process can be adjusted according to different biomass raw material characteristics; on the other hand, the biomass charcoal produced by medium-temperature pyrolysis has high yield, the proportion of biomass charcoal in pyrolysis products is higher, and the biomass charcoal maintains a certain volatile component proportion (less than or equal to 30 percent, preferably 10 to 30 percent), thereby being beneficial to promoting the reaction activity in the gasification process and reducing the gasification reaction temperature. The low-temperature pyrolysis treatment can lead the proportion of biomass charcoal generated in pyrolysis products to be higher, and certain volatile matters are reserved in the biomass charcoal, thereby being beneficial to subsequent gasification reaction; too high pyrolysis temperature can lead to more light components in biomass to separate out, can lead to the total proportion of biomass charcoal to be reduced, and the solid carbon component that contains in the biomass charcoal improves, and the volatile reduces, influences gasification reaction activity.
The volatile percentage of the biomass charcoal is preferably between 10% and 30%, and the volatile and oxygen react preferentially in the gasification furnace, so that the reaction is facilitated. When the pyrolysis temperature is higher than 500 ℃, the H element in the pyrolysis solid product can be quickly lost along with the temperature rise, and the volatile component ratio is continuously reduced, and when the pyrolysis temperature exceeds 600 ℃, the volatile component ratio is rapidly reduced to below 10%. The biochar prepared under the low-temperature condition has high volatile matter content, and ash components contained in the biochar are mainly low-melting ash, so that the operation temperature of the traditional gasifier can be reduced to 900-1000 ℃ above 1100 ℃.
The gas phase and liquid phase products biomass fuel gas and biomass tar after pyrolysis can be used as boiler fuel and enter a boiler to burn so as to provide heat; and meanwhile, boiler flue gas is generated by combustion, heat energy is provided for drying biomass particles, and the biomass raw material particles are dried. The biomass charcoal of the solid phase product after pyrolysis is taken as a gasification raw material, enters a gasification furnace, and is subjected to gasification reaction under the action of oxygen to prepare synthesis gas (the active ingredients of the synthesis gas are CO and H2); and the biomass charcoal which is a pyrolysis product can selectively produce part of charcoal base fertilizer as a byproduct, and can play a good role in carbon fixation, so that the method disclosed by the invention can achieve negative charcoal emission.
The pyrolysis temperature and the residence time of the biomass pyrolysis process can be adjusted according to different biomass raw material characteristics, and the heat of the pyrolysis process is generated by burning generated biomass fuel gas and biomass tar and self-heating. In the pretreatment process in the embodiment, the biomass raw material is 96.9t/h; biomass charcoal produced by pyrolysis is 33.9t/h, and the biomass charcoal yield is 35%. The method comprises the steps of carrying out a first treatment on the surface of the The total amount of biomass fuel gas and biomass tar was about 63t/h.
The volatile content of the biomass charcoal prepared by adopting the enthusiasm measurement is measured, and the calorific value of the biomass charcoal is measured by adopting an oxygen bomb method, wherein the measurement result is as follows: volatile 20%; calorific value-5700 kcal/kg (> 5500 kcal/kg).
The yield of the biomass charcoal prepared by the method is usually 20-40%; the volatile content is usually 10-30%; the calorific value is generally 4500-6500kcal/kg.
3. "boiler" treatment
The biomass gas and biomass tar which are pyrolysis products are sent into a high-pressure gas boiler with a fuel nozzle, the biomass gas and biomass tar are combusted in the boiler, and the generated heat heats cold water in the boiler to prepare high-temperature high-pressure water vapor, wherein the pressure of the water vapor is 9.8MPa (usually 9-10 MPa); the temperature is 540 ℃ (typically 500-540 ℃);
The high-temperature high-pressure water vapor produced by boiler treatment is used for driving an air compressor and other large compressors in the whole production process; the boiler flue gas generated by burning biomass fuel gas and biomass tar is used as a heat source for drying for biomass pretreatment; CO produced by combustion 2 And (3) discharging the waste gas from the high-pressure gas boiler, absorbing the waste gas by using an organic amine solution, and capturing and storing the waste gas.
The yield of high pressure steam generated in this example can reach about 145t/h.
The boiler is characterized in that biomass fuel gas and biomass tar are fully combusted under the action of excessive air, and the generated heat is used for generating high-pressure steam. The oil and the gas become CO after being burnt 2 、H 2 O、N 2 And (3) exhausting the flue gas of NOx. The combustion temperature of the boiler hearth is generally 800-1200 ℃, and the micro-positive pressure operation is carried out (10-20 kpa); the water pipe is communicated with a steam drum at the top of the hearth through heat exchange of a circulating water pipe arranged at the hearthHigh-pressure saturated steam is generated in the steam drum, and the heat after combustion generates high-temperature high-pressure steam (9.8 MPa,540 ℃) by indirectly heating cold water; the saturated steam is superheated by the boiler flue gas to generate high-pressure superheated steam; steam generated by the boiler is sent to each driving user through a pipeline. For example, the driving steam used as a large compressor in the air separation process ensures that the main energy source for air separation is renewable energy (steam generated by biomass fuel).
CO produced by "boiler" treatment 2 CO-rich gas removed by boiler flue gas and subsequent purifying device 2 The gas is absorbed with an organic amine solution and stored. The absorption of carbon dioxide by organic amine solution belongs to the physical and chemical comprehensive absorption method. Will contain CO 2 Is introduced into organic amine solution, and the organic amine adsorbs and traps CO 2 The temperature of the organic amine solution is 50-130 ℃; CO absorption 2 The organic amine solution is heated and regenerated, and CO 2 Re-precipitation to obtain CO with purity of more than 99% 2 . Captured CO 2 The raw material gas is used. The method for regenerating the amine liquid comprises the following steps: besides decompression flash evaporation and gas stripping, heating is also needed to thoroughly release the acid gas. The organic amine solution is MEA (ethanolamine) or MDEA (N-methyldiethanolamine), preferably MDEA.
The temperature of the organic amine solution is 100 ℃, and the trapped CO is 2 The purity of (2) is 99.5%; about 3kg/tCO per amine liquid consumption 2 (per ton of CO) 2 3kg of organic amine solution was consumed).
4. Space division treatment
The high-pressure water vapor obtained by the boiler treatment is used as driving vapor for air separation, and is subjected to air separation treatment to obtain high-pressure oxygen through separation, wherein the purity of the obtained high-pressure oxygen is 99.6 percent (usually more than or equal to 99.5 percent); the relative pressure of the high-pressure oxygen is 6MPa (usually 5.0-7.5 MPa);
The air separation refers to obtaining oxygen, nitrogen and other gases through air separation, and the air separation mainly comprises the key steps of air filtration purification, compression-expansion refrigeration, cold box separation and the like, wherein a compressor in the compression-expansion refrigeration process is main energy consumption equipment in an air separation process, and the air separation process can be driven by a steam turbine or a motor.
According to the method, the hollow partial pressure compressor unit is driven by steam, the steam is from a boiler using biomass gas and biomass fuel oil as fuels, the main energy of the whole air separation can be ensured to be renewable energy, and the whole production process is a green sustainable production process.
5. Gasification treatment
Delivering high-pressure oxygen obtained by biomass charcoal and air separation treatment into a high-pressure powder coal gasification furnace, carrying out gasification treatment under high-temperature and high-pressure conditions, and carrying out oxidation-reduction reaction on the biomass charcoal and oxygen in the gasification furnace together to generate crude synthesis gas (CO+H) 2 ) And sodium-potassium-containing ash, wherein the active ingredients in the crude synthesis gas are CO and H 2 The method comprises the steps of carrying out a first treatment on the surface of the The ash slag containing sodium and potassium can be used as a compound fertilizer additive; wherein, the ratio of the mass of the biomass charcoal to the volume of oxygen in a standard state is 200:100 (kg/m) 3 ) (typically (167-200): 100 (kg/m) 3 ) A) is provided; the gasification treatment temperature is 950 ℃ (typically 900-1000 ℃); the relative pressure of gasification treatment is 6.0MPa (usually 3.5-6.5 MPa), and the treatment time is 10s (usually 8-12 s).
H in raw synthesis gas 2 The volume ratio of (a) is approximately 23-30% (dry basis), and the volume ratio of CO is approximately 60-67% (dry basis). In the embodiment, the biomass charcoal is 33.9t/h in the gasification treatment process; the oxygen content was 17000Nm 3 /h; the effective gas amount of the prepared crude synthesis gas is 56500Nm 3 /h; the yield of the ash slag containing sodium and potassium as byproducts is 3t/h;
the biomass charcoal contains a small amount of light components (hydrocarbon oxygen compounds), water in the gasification furnace participates in the reaction, or directly sprays water, or exists in the form of stored chilled water at the lower part of the gasification furnace, and the biomass charcoal reacts with high-pressure oxygen to generate CO and H 2 。
The biomass charcoal and oxygen sent from the upstream are sprayed into the furnace body through a nozzle (burner) of the gasification furnace, high-temperature high-pressure oxidation-reduction reaction is rapidly carried out, a spray chilling device and a chilled water level are arranged at the lower part of the gasification furnace, slag in the synthesis gas is cooled mainly through a water bath method, and part of chilled water is also involved in the reaction process; the synthesis gas after water bath (main component isCO、H 2 、CO 2 、H 2 O, dust) is sent out of the gasification furnace, is washed by a venturi scrubber and a washing tower in the gasification process, and is further dedusted and then sent to the downstream conversion process.
The volatile matter generally contains various organic alkane and alcohol ester ether substances, has low ignition point and high reaction activity, is easy to react with oxygen introduced into the gasification furnace, and has the reaction speed far exceeding the reaction of solid carbon and oxygen, so that a certain volatile matter proportion is reserved in biomass carbon, the gasification reaction is promoted, and the gasification reaction temperature is reduced.
6. Syngas shift processing
Feeding the crude synthetic gas into a shift converter, carrying out synthetic gas shift treatment by adopting a wide-temperature sulfur-resistant isothermal shift process, and regulating CO and H in the crude synthetic gas 2 Is prepared into the conversion synthetic gas;
during the conversion treatment of the synthesis gas, H in the synthesis gas is converted 2 And CO volume ratio, the corresponding H is adjusted according to the green chemicals 2 And the volume ratio of CO.
The raw synthesis gas generally also contains CO 2 、CH 4 、N 2 And sulfide and other impurity components, and the content of CO in the effective components is high, and the aim of transformation is mainly to react CO in the crude synthesis gas with water vapor to generate carbon dioxide and hydrogen. Reducing the content of CO in the crude synthesis gas, and generating CO 2 Absorbed by the organic amine solution.
The shift reaction is a reversible exothermic reaction, the reaction is more intense under the action of the catalyst, and simultaneously, a large amount of heat is released, and the equilibrium conversion rate is continuously reduced along with the increase of the temperature. The CO content in the crude synthesis gas can generally reach more than 60%, the heat insulation temperature rise of the shift reaction is larger due to higher CO content, in order to obtain higher conversion rate, the index of lower CO content of a shift outlet (for example, the CO content of raw material gas needed for synthesizing methanol needs to be reduced to about 33 percent) is ensured, and the reaction heat is required to be continuously removed, so the shift reaction is generally carried out in multiple stages, and the core equipment of the shift reaction is a shift converter and a heat exchanger;
Because the shift reaction is a catalytic reaction, the sulfur-containing component in the crude synthesis gas is easy to cause the catalyst to be deactivated in the sulfur environment, so that the sulfur-resistant catalyst is required to be selected aiming at the problem of the catalyst deactivation in the sulfur environment.
The wide temperature sulfur tolerant isothermal shift process shift-treating the raw syngas is a conventional treatment process in the art.
Isothermal conversion is an improved process for traditional adiabatic conversion, and the isothermal conversion furnace replaces heat pipes in the catalyst bed to maintain the temperature balance of the bed by timely removing heat generated by the reaction. In the isothermal conversion process, the reaction heat is directly taken away by the steam generated by the steam drum connected with the conversion furnace, so that the conversion reaction temperature is reduced. Compared with the traditional adiabatic conversion process, the isothermal conversion can effectively control the reaction temperature of the conversion furnace to be carried out at a proper temperature; the method effectively ensures wider adaptability to temperature in the conversion reaction process, mild reaction, reduces the number of required conversion sections, reduces the resistance drop of the synthesis gas, and is a safe, reliable and energy-saving conversion process.
The reaction temperature of the shift, especially the first stage shift furnace (which needs to bear the highest temperature), is generally controlled to be 180-350 ℃, lower than that of the traditional adiabatic shift first stage shift furnace (generally above 450 ℃), and the operating pressure is generally slightly lower than that of the raw synthesis gas sent by gasification.
The degree of shift is related to the requirements of the downstream chemical synthesis process, typically shifting H in the synthesis gas 2 And the volume ratio of CO the requirement is (1.5- ≡): 1, (e.g., methanol is 2.05:1; ammonia is all converted to H) 2 ) The method comprises the steps of carrying out a first treatment on the surface of the H generally according to downstream product requirements 2 And the CO proportion to set the number of sections of the conversion flow, namely the number of conversion furnaces.
In this example, the synthesis of green methanol is taken as an example, and H in the synthesis gas is adjusted and changed 2 And the volume ratio of CO is 2.05:1.
7. purifying treatment
Cooling the prepared conversion synthesis gas to room temperature, introducing the cooled conversion synthesis gas into a cold methanol solution in a reaction tower, and purifying the conversion synthesis gas by adopting a low-temperature methanol washing process to prepare clean synthesis gas (also called as purified gas); wherein the temperature is-40+ -5deg.C (usually-55deg.C to-35deg.C)) Takes methanol as an absorption solvent, and removes acid gas (CO) in raw material gas by utilizing the characteristic of extremely high solubility of the methanol to the acid gas at low temperature 2 And sulfides); to obtain a product containing H only 2 And net synthesis gas for CO.
CO in clean syngas 2 Less than 20ppm of H 2 The S content is less than 0.1ppm. And (3) converting the sulfur-containing gas of the synthesis gas after the purification treatment, and carrying out sulfur recovery treatment to prepare a sulfur product.
The purification treatment adopts a low-temperature methanol washing process: the low-temperature methanol washing process is suitable for treating CO in gas 2 And sulfide removal, wherein the process is a typical physical absorption method, and takes cold methanol (-55 ℃ to minus 35 ℃) as an absorption solvent, and utilizes the characteristic of extremely high solubility of the methanol to acid gas at low temperature to remove the acid gas in the raw gas. The process gas has high purification degree, and can change CO in the outlet synthesis gas 2 Is taken off to less than 20ppm, H 2 S is less than 0.1ppm, and the desulfurization and decarbonization of the gas can be performed in stages in the same column or in different columns selectively.
The clean syngas amount after the clean treatment in this example was 56500Nm 3 /h(H 2 And CO); wherein H in the clean synthesis gas 2 And the volume ratio of CO is 2.05:1.
the low temperature methanol washing process is suitable for treating CO contained in gas 2 And sulfide removal, which is a conventional and typical physical absorption method in the field, takes cold methanol (-55 ℃ to minus 35 ℃) as an absorption solvent, and removes acid gas in raw gas by utilizing the characteristic of extremely high solubility of methanol to the acid gas at low temperature. Desulfurization and decarbonization (CO) of gases 2 ) Optionally in the same column section or in different columns.
The sulfur-containing gas in the shift conversion synthesis gas is removed by using the Claus method, and the shift conversion synthesis gas is purified. Absorbing CO removed from the shift synthesis gas by using organic amine solution absorption method 2 Capturing and storing CO with an organic amine solution 2 . Absorption of CO by organic amine solutions 2 CO of the "boiler" treatment step and the treatment method of (c) 2 The absorption is the same.
8. Synthesis treatment
8A) The clean synthesis gas is sent into a synthesis tower (enters a synthesis treatment process) to be subjected to synthesis treatment, and green chemicals are prepared.
Synthesizing raw material gas into green chemicals under the action of a catalyst, wherein the raw material gas is purified clean synthesis gas, and CO which is discharged by the 'boiler' treatment and the purification treatment and is absorbed and trapped by an organic amine solution 2 And hydrogen.
The corresponding synthesis treatments were performed according to the different green chemistry methods. In the embodiment, taking the synthesis of green methanol as an example, the methanol synthesis is generally carried out under the conditions of 5-10 MPa pressure, 200-300 ℃ and catalyst, and the methanol yield is more than 98%. The clean synthesis gas enters a synthesis process to synthesize the product methanol of 25t/h.
The method of the invention can synthesize green fuel oil, ethanol, ammonia, methane and glycol besides green methanol, and different chemicals need different operation conditions and catalysts, which are generally mature industrial technologies and are not described herein.
8B) Capturing CO discharged from boiler treatment and purification treatment into storage tank by organic amine solution method 2 React with hydrogen to synthesize green chemical.
In this example, the synthesis of methanol is taken as an example, and most of CO discharged from the boiler treatment and the purification treatment is 2 Is captured into a storage tank (30000 Nm) by an organic amine solution method 3 And/h) as a raw material gas with hydrogen (green hydrogen (. About.90000 Nm fed from the outside) 3 And/h)) are conveyed to a synthesis reactor together, mixed and methanol is generated to 42.9t/h under the action of a catalyst.
CO 2 The synthesis step for preparing methanol by hydrogenation is carried out according to a method known in the art, for example, generally under about 7MPa and about 300 ℃ under the condition of a catalyst, and the methanol yield is as high as 98.5% or more.
The electricity used in all production processes in the invention comes from renewable electricity (green electricity such as wind, light, water and the like). Meanwhile, renewable energy sources such as wind, light, water and the like are adopted to generate green hydrogen (hydrogen) which is produced by the electrolytic cell equipment.
The method comprehensively utilizes biomass raw materials in a classified manner, the method for preparing the green chemical product is a green carbon-negative process, carbon in the biomass raw materials is solidified into products (such as methanol, fuel oil, glycol and the like) through a series of reaction processes, and only a small amount of CO is generated due to the trapping efficiency 2 Discharged to the atmosphere by flue gas, but because the raw material is biomass, this part of the CO is discharged to the atmosphere 2 Essentially zero carbon process, without increasing carbon emissions from the atmosphere.
The bamboo scraps contain very low sulfur elements, so that the sulfur recovery process is negligible, and almost no sulfur byproducts are produced. All the electricity used in the production process comes from renewable electricity (green electricity) sent from the grid.
Example 2
Except in the pyrolysis treatment process, the pyrolysis temperature is 350 ℃, and the pyrolysis time is 10min; the volatile matter of the biomass charcoal is 30%; the gasification treatment temperature is 900 ℃; the remainder was the same as in example 1.
Biomass charcoal calorific value-5800 kcal/kg, charcoal yield about 35%, and required biomass about 95.2t/h.
Example 3
Except in the pyrolysis treatment process, the pyrolysis temperature is 500 ℃ and the pyrolysis time is 30min; the volatile matter of the biomass charcoal is 10%; the gasification treatment temperature is 1000 ℃; the remainder was the same as in example 1.
Biomass charcoal calorific value-5600 kcal/kg, charcoal yield about 30%, and required biomass about 115t/h.
As described above, exemplary embodiments of the present invention are described in detail with reference to the accompanying drawings. It should be understood that the invention is not intended to be limited to these specific details as set forth in the following description. Equivalent or similar changes to the structure and features of the exemplary embodiments may be made without departing from the spirit and scope of the present invention, which changes will also fall within the protection scope of the invention as defined in the appended claims.
Claims (9)
1. A method for preparing green chemicals by biomass split utilization, which is characterized by comprising the steps of carrying out pyrolysis treatment on biomass raw materials; gasifying biomass charcoal and oxygen which are pyrolysis products to prepare synthesis gas; and (3) regulating the gas composition ratio of the gasified synthetic gas, and then carrying out synthesis treatment to obtain the green chemical.
2. The method of claim 1, wherein the pyrolysis treatment is low temperature pyrolysis, wherein the pyrolysis treatment temperature is less than or equal to 500 ℃.
3. The method of claim 1 or 2, wherein the gasification treatment temperature is 900 to 1000 ℃; the relative pressure is 3.5-6.5 MPa.
4. The method according to claim 1 or 2, further comprising a shift treatment of the synthesis gas generated by the gasification treatment, wherein the synthesis treatment is performed after adjusting the gas composition ratio.
5. A method for preparing green chemicals by fractional utilization of biomass, comprising the steps of:
1) Pretreatment of
Pretreating a biomass raw material to obtain a pretreated biomass material with a water content of less than 15% and a particle size of less than 5 cm;
2) Pyrolysis treatment
Carrying out pyrolysis treatment on the pretreated biomass material, and carrying out pyrolysis to generate biomass fuel gas, biomass tar and biomass charcoal;
3) Preparation of high-temperature high-pressure steam
The biomass fuel gas and the biomass tar are sent into a steam boiler to be subjected to boiler treatment, namely the biomass fuel gas and the biomass tar are combusted in the boiler to provide heat, and water in the boiler is heated to prepare high-temperature and high-pressure water vapor;
4) Space division treatment
The high-temperature high-pressure water vapor prepared by the boiler is used as driving vapor of a compressor, and air separation treatment is carried out to obtain high-pressure oxygen for later use;
5) Gasification treatment
Gasifying high-pressure oxygen prepared by biomass charcoal and air separation under high-temperature and high-pressure conditions, wherein the biomass charcoal, oxygen and water react to prepare crude synthesis gas and ash containing sodium and potassium, and the active ingredients in the crude synthesis gas are CO and H 2 ；
6) Transformation process
The conversion treatment is carried out on the crude synthesis gas, and CO and H in the crude synthesis gas are regulated 2 To obtain a conversion synthesis gas;
7) Purifying treatment
Purifying the shift synthesis gas to remove sulfur and CO in the shift synthesis gas 2 Producing a net synthesis gas such that the net synthesis gas contains only CO and H 2 ；
8) Synthesis treatment
Synthesizing the clean synthesis gas under high pressure and catalysis conditions, and carrying out CO and H 2 Chemical reaction occurs to synthesize green chemicals.
6. The method of claim 5, wherein the pyrolysis treatment in step 2) is performed at a temperature of 500 ℃ or less; pyrolysis time is 10-30min.
7. The method according to claim 5 or 6, wherein the volatile content of the biomass charcoal of the pyrolysis product in step 2) is less than or equal to 30%, preferably 10-30%.
8. The method according to claim 5 or 6, wherein the gasification process in step 5) is carried out at a temperature of 900-1000 ℃; the relative pressure of gasification treatment is 3.5-6.5MPa.
9. The method of claim 5 or 6, further comprising the step of absorbing CO by the organic amine solution produced by combustion of the biomass gas and biomass tar during the "boiler" treatment of step 3) 2 The method comprises the steps of carrying out a first treatment on the surface of the CO absorbed by organic amine solution removed during clean-up treatment of shifted synthesis gas 2 And H 2 And (3) reacting to synthesize the green chemical.
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