CN116477570A - Device and method for preparing hydrogen from household garbage and/or organic matters - Google Patents
Device and method for preparing hydrogen from household garbage and/or organic matters Download PDFInfo
- Publication number
- CN116477570A CN116477570A CN202310485108.3A CN202310485108A CN116477570A CN 116477570 A CN116477570 A CN 116477570A CN 202310485108 A CN202310485108 A CN 202310485108A CN 116477570 A CN116477570 A CN 116477570A
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- China
- Prior art keywords
- hydrogen
- gas
- equipment
- liquid
- furnace
- 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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Links
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 464
- 239000001257 hydrogen Substances 0.000 title claims abstract description 463
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 394
- 239000010813 municipal solid waste Substances 0.000 title claims abstract description 66
- 238000000034 method Methods 0.000 title claims abstract description 58
- 239000007789 gas Substances 0.000 claims abstract description 291
- 239000007788 liquid Substances 0.000 claims abstract description 191
- 238000000197 pyrolysis Methods 0.000 claims abstract description 179
- 238000002309 gasification Methods 0.000 claims abstract description 125
- 238000003860 storage Methods 0.000 claims abstract description 124
- 238000010438 heat treatment Methods 0.000 claims abstract description 111
- 239000005416 organic matter Substances 0.000 claims abstract description 100
- 238000000926 separation method Methods 0.000 claims abstract description 99
- 238000006243 chemical reaction Methods 0.000 claims abstract description 73
- 238000000746 purification Methods 0.000 claims abstract description 67
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 66
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 63
- 238000004519 manufacturing process Methods 0.000 claims abstract description 45
- 238000001816 cooling Methods 0.000 claims abstract description 41
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000002737 fuel gas Substances 0.000 claims abstract description 35
- 239000002918 waste heat Substances 0.000 claims abstract description 34
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 29
- 238000006477 desulfuration reaction Methods 0.000 claims abstract description 27
- 230000023556 desulfurization Effects 0.000 claims abstract description 26
- 238000005336 cracking Methods 0.000 claims description 97
- 239000012071 phase Substances 0.000 claims description 67
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 44
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 38
- 239000000463 material Substances 0.000 claims description 35
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- 238000002485 combustion reaction Methods 0.000 claims description 24
- 239000003054 catalyst Substances 0.000 claims description 22
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 22
- 239000002893 slag Substances 0.000 claims description 21
- 239000001569 carbon dioxide Substances 0.000 claims description 19
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 19
- 238000010521 absorption reaction Methods 0.000 claims description 18
- 239000003921 oil Substances 0.000 claims description 17
- 235000019198 oils Nutrition 0.000 claims description 17
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 16
- 239000000295 fuel oil Substances 0.000 claims description 15
- 239000012528 membrane Substances 0.000 claims description 15
- 239000011269 tar Substances 0.000 claims description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 13
- 238000005516 engineering process Methods 0.000 claims description 13
- 229910052760 oxygen Inorganic materials 0.000 claims description 13
- 239000001301 oxygen Substances 0.000 claims description 13
- 230000005855 radiation Effects 0.000 claims description 13
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- 239000000446 fuel Substances 0.000 claims description 12
- 239000003546 flue gas Substances 0.000 claims description 11
- 238000006356 dehydrogenation reaction Methods 0.000 claims description 10
- 239000010802 sludge Substances 0.000 claims description 10
- 238000001179 sorption measurement Methods 0.000 claims description 10
- 229910000831 Steel Inorganic materials 0.000 claims description 9
- 239000002131 composite material Substances 0.000 claims description 9
- 238000007599 discharging Methods 0.000 claims description 9
- 239000010959 steel Substances 0.000 claims description 9
- 229910052742 iron Inorganic materials 0.000 claims description 8
- 239000010815 organic waste Substances 0.000 claims description 8
- 238000009834 vaporization Methods 0.000 claims description 8
- 230000008016 vaporization Effects 0.000 claims description 8
- 239000000428 dust Substances 0.000 claims description 7
- 239000006148 magnetic separator Substances 0.000 claims description 7
- 238000011084 recovery Methods 0.000 claims description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- 239000007791 liquid phase Substances 0.000 claims description 6
- 239000010902 straw Substances 0.000 claims description 6
- 230000003009 desulfurizing effect Effects 0.000 claims description 5
- 238000000605 extraction Methods 0.000 claims description 5
- 239000003208 petroleum Substances 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 239000002826 coolant Substances 0.000 claims description 4
- 241000931143 Gleditsia sinensis Species 0.000 claims description 3
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 3
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- 239000010775 animal oil Substances 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 230000003139 buffering effect Effects 0.000 claims description 3
- 230000002349 favourable effect Effects 0.000 claims description 3
- 229910052987 metal hydride Inorganic materials 0.000 claims description 3
- 150000004681 metal hydrides Chemical class 0.000 claims description 3
- 239000003027 oil sand Substances 0.000 claims description 3
- 238000005191 phase separation Methods 0.000 claims description 3
- 239000010773 plant oil Substances 0.000 claims description 3
- 239000013049 sediment Substances 0.000 claims description 3
- 239000002689 soil Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 239000004575 stone Substances 0.000 claims description 3
- 238000003786 synthesis reaction Methods 0.000 claims description 3
- 235000015112 vegetable and seed oil Nutrition 0.000 claims description 3
- 239000008158 vegetable oil Substances 0.000 claims description 3
- 238000009423 ventilation Methods 0.000 claims description 3
- 239000011280 coal tar Substances 0.000 claims description 2
- 238000006298 dechlorination reaction Methods 0.000 claims description 2
- 238000011068 loading method Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000011368 organic material Substances 0.000 claims description 2
- 238000007873 sieving Methods 0.000 claims description 2
- 238000009833 condensation Methods 0.000 abstract description 7
- 230000005494 condensation Effects 0.000 abstract description 7
- 239000000047 product Substances 0.000 description 59
- 239000002699 waste material Substances 0.000 description 16
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 15
- 229910052799 carbon Inorganic materials 0.000 description 12
- 239000000126 substance Substances 0.000 description 11
- 239000004215 Carbon black (E152) Substances 0.000 description 10
- 229930195733 hydrocarbon Natural products 0.000 description 10
- 150000002430 hydrocarbons Chemical class 0.000 description 10
- 239000002023 wood Substances 0.000 description 10
- 239000002994 raw material Substances 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- 239000004033 plastic Substances 0.000 description 6
- 229920003023 plastic Polymers 0.000 description 6
- 239000002028 Biomass Substances 0.000 description 5
- 239000002956 ash Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 239000011276 wood tar Substances 0.000 description 5
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 230000009977 dual effect Effects 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- 239000011949 solid catalyst Substances 0.000 description 4
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- DPFFXSPEODLYOH-UHFFFAOYSA-N bis($l^{1}-oxidanyl)methanone Chemical compound [O]C([O])=O DPFFXSPEODLYOH-UHFFFAOYSA-N 0.000 description 3
- 229910000514 dolomite Inorganic materials 0.000 description 3
- 239000010459 dolomite Substances 0.000 description 3
- 239000003502 gasoline Substances 0.000 description 3
- 239000004519 grease Substances 0.000 description 3
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 3
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 3
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 3
- 239000003345 natural gas Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000005060 rubber Substances 0.000 description 3
- 239000010920 waste tyre Substances 0.000 description 3
- 244000025254 Cannabis sativa Species 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000002283 diesel fuel Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 239000013067 intermediate product Substances 0.000 description 2
- 239000010806 kitchen waste Substances 0.000 description 2
- 244000144972 livestock Species 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- BXGYYDRIMBPOMN-UHFFFAOYSA-N 2-(hydroxymethoxy)ethoxymethanol Chemical compound OCOCCOCO BXGYYDRIMBPOMN-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000010828 animal waste Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000000382 dechlorinating effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- -1 diesel Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000010791 domestic waste Substances 0.000 description 1
- 210000003746 feather Anatomy 0.000 description 1
- 210000003608 fece Anatomy 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000010763 heavy fuel oil Substances 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 244000144977 poultry Species 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 238000004227 thermal cracking Methods 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
- 235000021419 vinegar Nutrition 0.000 description 1
Classifications
-
- 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
- C01B3/22—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
- B01D53/04—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
- B01D53/047—Pressure swing adsorption
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
- B01D53/1425—Regeneration of liquid absorbents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
- B09B3/40—Destroying solid waste or transforming solid waste into something useful or harmless involving thermal treatment, e.g. evaporation
-
- 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
- C01B3/0005—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes
- C01B3/001—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes characterised by the uptaking medium; Treatment thereof
- C01B3/0015—Organic compounds; Solutions thereof
-
- 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
-
- 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
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/22—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds
- C01B3/24—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds of hydrocarbons
- C01B3/26—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds of hydrocarbons 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
- C01B3/501—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by diffusion
-
- 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
- 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
- C01B3/56—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with solids; Regeneration of used solids
-
- 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
-
- 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
- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
- C10G1/10—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal from rubber or rubber waste
-
- 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
- C10J3/02—Fixed-bed gasification of lump fuel
- C10J3/20—Apparatus; Plants
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Analytical Chemistry (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention relates to a device and a method for preparing hydrogen from household garbage and/or organic matters, wherein the device mainly comprises pretreatment equipment, a feeder, a pyrolysis gasification furnace, a high-temperature pyrolysis furnace, a waste heat steam boiler, desulfurization equipment, conversion hydrogen production equipment, gas-liquid separation equipment, liquid collection equipment, gas purification equipment, hydrogen separation and purification equipment, a heating furnace, a gas storage tank, a compressor, hydrogen storage equipment, a condenser, an organic liquid or organic gas storage tank and a delivery pump; the method comprises the following steps: pretreatment, pyrolysis gasification, high-temperature pyrolysis, cooling and desulfurization, hydrogen production by conversion, condensation separation and purification of hydrogen-rich fuel gas, hydrogen purification and hydrogen storage; the invention directly cracks garbage or organic matter pyrolysis gas phase products into hydrogen and carbon monoxide under the action of water vapor at 1000-1300 ℃, hydrogen-rich gas is obtained through conversion reaction, and the invention 'liquid organic matter carrier' is used for purifying hydrogen and storing hydrogen, so that the domestic garbage and organic matter are used for preparing hydrogen with the purity of 99.99 percent.
Description
Technical Field
The invention relates to the technical field of hydrogen preparation from household garbage and organic matters, and belongs to a device and a method for preparing hydrogen from garbage and/or organic matters.
Background
In CN115386400A, a system and a method for preparing hydrogen from organic garbage, the hydrogen is extracted by pyrolysis of the organic garbage in a fluidized bed pyrolysis gasification furnace, wherein the gasification furnace comprises a fixed bed gasification furnace, a fluidized bed gasification furnace and a gas flow bed gasification furnace; in the above-mentioned gasification furnace, it is known that the time for the gas after pyrolysis of the material to flow through the high-temperature combustion zone is short, the thermal cracking degree of the material is low, and the discharged gas is condensed to produce a large amount of hydrocarbon oil (C) 5 -C 25 ) And biomass tar (containing wood vinegar and wood tar), while the yield of non-condensable gas phase is low, and the non-condensable gas phase contains other gases (such as CO and CO) with a large amount of non-hydrogen components 2 、CH 4 、C 2 -C 4 ) Resulting in the conversion of the organic waste material into hydrogen (H) 2 ) The yield of the PSA system is low, and the hydrogen separation and purification cost of the PSA system in the subsequent working procedure is high; in CN113913203A, a method for preparing hydrogen from organic garbage, it is disclosed that 8% of carbide slag, dolomite and iron block catalyst are added into crushed organic garbage to prepare RDF fuel or The fuel rod and the RDF combustion rod are subjected to anaerobic pyrolysis treatment in the rotary kiln to obtain heavy tar and mixed gas, the tail gas after combustion is treated by adopting a washing tower A and a washing tower B, and CO in the tail gas is absorbed by adopting a CuCL ammonia water solution so as to lead the environment-friendly emission to reach the standard, and the process flow is complex and the treatment cost is high; in particular, the rotary kiln is internally overlapped to 1000 ℃ to carry out RDF pyrolysis, the outer wall of the rotary kiln is required to be heated by far 1000 ℃ outside the kiln wall, the outer wall of the rotary kiln is easy to be deformed and damaged by high-temperature heating, the industrial production is difficult, and the energy consumption is high; in the rotary kiln, solid catalysts such as carbide slag, dolomite and iron blocks are not easy to fully contact with a pyrolyzed heavy tar gas-phase product, gas-phase-solid-phase catalytic reaction is not easy to occur, the heavy tar is difficult to be catalytically decomposed into hydrogen, the solid catalysts such as carbide slag, dolomite and iron blocks are not scientific and effective CO conversion catalysts, in the rotation of the rotary kiln, the contact time of flowing gas-phase substances and the solid catalysts is short, and carbon monoxide and water vapor generated by pyrolysis are difficult to be converted into hydrogen and carbon dioxide by conversion reaction; the final product contains light tar, the light tar (containing H element) is not converted into hydrogen, and the conversion rate of preparing hydrogen from organic garbage is reduced; in particular, the hydrogen product treated by the washing tower A and the washing tower B also contains a large amount of other small molecular organic gas components (such as CH 4 ，C 2 -C 5 ) The purity of the product hydrogen is low, and the industrial applicability is poor; in CN 206318700U, the system for producing hydrogen from garbage, the garbage is pyrolyzed in a pyrolysis device, high-temperature oil gas generated by pyrolysis is condensed and separated from oil and water, and fuel gas, light oil and heavy oil after oil and water separation are respectively supplied to a pyrolysis gas pyrolysis chamber and a pyrolysis oil pyrolysis chamber in a pyrolysis device for pyrolysis treatment to produce hydrogen; the high-temperature oil gas discharged after the pyrolysis of the garbage is subjected to cooling condensation and oil-water separation to obtain intermediate products of room temperature fuel gas, light oil, heavy oil and the like, and the intermediate products of the light oil, the heavy oil and the like are heated and raised from room temperature to high temperature again to implement high-temperature pyrolysis hydrogen production, namely, the temperature is lowered from the high temperature to the room temperature and then raised from the room temperature to the high temperature, so that the energy consumption cost of hydrogen production is greatly increased, the process flow is long, and the investment is large; in particular, heavy oils are present which crack tightly at high temperaturesHeavy coking, plugging equipment pipelines and plugging solid catalysts.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides an improved device and a method for preparing hydrogen from household garbage and/or organic matters, wherein the device consists of pretreatment equipment, a feeder, a pyrolysis gasification furnace, a pyrolysis furnace, a waste heat steam boiler, desulfurization equipment, conversion hydrogen production equipment, gas-liquid separation equipment, liquid collection equipment, gas purification equipment, hydrogen separation and purification equipment, a heating furnace, a gas storage tank, a compressor, hydrogen storage equipment, a condenser, an organic liquid or organic gas storage tank, a delivery pump, a valve I and a valve II;
The method is characterized in that: the method comprises the steps that combustible materials selected from household garbage and/or organic matters are connected and communicated with a feeder inlet of a pyrolysis gasification furnace through a conveying system by utilizing pretreatment equipment, a gas-phase product outlet of the pyrolysis gasification furnace is connected and communicated with a valve III inlet, a valve II outlet is respectively connected and communicated with a valve I outlet and a heating cracking pipe inlet in a high-temperature pyrolysis furnace, a discharge port of an organic liquid or organic gas storage tank is connected and communicated with an inlet of a conveying pump through a pipeline, and an outlet of the conveying pump is connected and communicated with an inlet of the valve I through a pipeline; the heating cracking pipe outlet in the high-temperature cracking furnace is connected and communicated with the flue gas heating chamber inlet of the waste heat steam boiler through a first pipeline, the flue gas heating chamber outlet of the waste heat steam boiler is connected and communicated with the inlet of the gas-liquid separation device through a pipeline, the steam outlet of the waste heat steam boiler is connected and communicated with the pipeline through a first steam pipe, the steam outlet of the waste heat steam boiler is connected and communicated with the upper part of the conversion catalyst in the conversion hydrogen production device through a second steam pipe, the conversion hydrogen production device belongs to a fixed bed structure, the solid conversion catalyst is arranged on a sieve plate in the middle of the conversion hydrogen production device, the discharge port in the lower part of the conversion hydrogen production device is connected and communicated with the material inlet of the condenser through a pipeline, the material outlet of the condenser is connected and communicated with the inlet of the gas-liquid separation device through a pipeline, the gas outlet in the upper part of the gas-liquid separation device is connected and communicated with the gas inlet of the gas purification device through a second pipeline, and the bottom of the gas-liquid separation device is provided with the liquid outlet through a pipeline and communicated with the inlet of the liquid collection device; the outlet of the gas purifying device is communicated with the inlet of the first compressor through a pipeline, the outlet of the first compressor is communicated with the inlet of the hydrogen separating and purifying device through a pipeline, the outlet of pure hydrogen of the hydrogen separating and purifying device is communicated with the inlet of the second compressor through a pipeline, the outlet of the second compressor is communicated with the inlet of the hydrogen storage device through a pipeline, and the other gas outlets of the hydrogen separating and purifying device are communicated with the inlet of the gas storage tank through gas pipelines; the outlet of the fuel gas storage tank is communicated with the fuel inlet of the heating furnace through a pipeline; the flue gas outlet after combustion of the heating furnace is connected and communicated with the inlet of the heating chamber of the high-temperature cracking furnace through a flue built by high-temperature weather-resistant materials;
The pretreatment equipment comprises a garbage grab bucket machine, a bag breaking machine, a sorting machine, a magnetic separator and a dryer, belongs to a common garbage pretreatment device of a household garbage incineration power plant, and comprises the steps of feeding, bag breaking and sorting household garbage through the grab bucket machine to remove ironware and soil to obtain organic garbage, and drying the organic garbage to obtain pretreated combustible;
the feeding machine belongs to a hydraulic reciprocating feeding machine, a screw conveyor or a known garbage feeding machine;
the organic liquid or organic gas storage tank belongs to a pressure-resistant steel fuel storage tank in petrochemical industry;
the conveying pump belongs to an explosion-proof gas conveying pump or a liquid conveying pump used in petrochemical industry;
the pyrolysis gasification furnace is one gasification furnace selected from (1) a vertical or horizontal anaerobic pyrolysis gasification furnace with a stirring device, and (2) a pyrolysis gasification furnace with air (or oxygen) as a gasifying agent; comprises a fixed bed gasification furnace, a fluidized bed gasification furnace and an air flow bed gasification furnace, preferably a fixed bed gasification furnace, wherein the fixed bed gasification furnace is divided into a drying zone, a pyrolysis zone, a combustion zone, a still wish zone and a lower slag discharging zone; after the garbage materials enter the gasification furnace, the garbage materials are firstly dried due to higher water content, the drying energy is derived from the heat release of the combustion zone, and then the garbage materials enter the pyrolysis zone, and the pyrolysis is started to generate gas in the pyrolysis zone; the combustion zone provides energy for the whole system, the pyrolyzed carbon is fully mixed with gasifying agent (air or oxygen) fed by a nozzle for violent combustion, water and carbon dioxide are generated, and heat is released; in the reduction zone, water and carbon dioxide undergo a reduction reaction with pyrolyzed carbon to be converted into carbon monoxide and hydrogen, gas phase products discharged from the pyrolysis gasification furnace are separated into small particle ash, slag or tar through a cyclone separator, then the small particle ash, slag or tar enters the next working procedure for treatment and utilization, and inorganic slag is discharged from the lower part of the pyrolysis gasification furnace;
The high-temperature cracking furnace belongs to a high-temperature cracking tube furnace in an anaerobic environment, adopts the principle of indirect heat supply, and utilizes a heating mode of radiation heat transfer and convection heat transfer; under the condition of isolating air, organic materials input into the high-temperature cracking furnace are subjected to carbon chain fracture or dehydrogenation under the high-temperature action; the main structure of the high-temperature cracking furnace comprises: the device comprises a radiation chamber, a convection chamber, a waste heat recovery cooling system, a burner and a ventilation system; such as SRT type cracking furnace of Rums company, USC type cracking furnace of S.W, millisecond vertical cracking furnace of Keloger company, GK-1 type cracking furnace of KTI company and CBL type cracking furnace of China;
the heating furnace belongs to a device for heating the high-temperature cracking furnace in the petrochemical industry, and can adopt gas heating, fuel oil heating and high-temperature plasma flame heating;
the waste heat steam boiler belongs to a tubular steam generator;
the desulfurization equipment belongs to gas desulfurization equipment in petrochemical industry;
the device for producing hydrogen by conversion belongs to the device for producing hydrogen and carbon trioxide by carbon monoxide and steam under the action of a catalyst (namely a conversion catalyst) in a fixed bed, such as the device for producing hydrogen by carbon monoxide conversion in the ammonia synthesis industry;
The gas-liquid separation equipment belongs to gas-phase and liquid-phase separation equipment used in petrochemical industry, the gas is discharged from the upper part of the equipment, and the liquid phase (such as oil and water) is discharged from a side wall pipe orifice valve at the lower part of the equipment;
the liquid collecting device belongs to an oil-water collecting and buffering tank in petrochemical industry;
the gas purifying equipment belongs to the gas purifying equipment in petrochemical industry, and has the functions of desulfurizing, dechlorinating, tar removing and dust removing, and comprises an alkaline washing tower, wherein alkali liquor reacts with acidic substances (such as sulfur dioxide, hydrogen sulfide, hydrogen chloride and carbon dioxide) in the gas to remove the acidic substances in the gas, and the dust in the gas is washed by liquid;
the hydrogen separation and purification equipment is one of the following equipment: (1) the hydrogen is extracted by adopting a single membrane separation device, (2) the hydrogen is extracted by adopting a single PSA pressure swing adsorption gas separation device, (3) the hydrogen is extracted by adopting a PSA device, and then the tail gas after the hydrogen is extracted by the PSA device is subjected to a further recovery device of the hydrogen extracted by the membrane separation device, so that the recovery rate of the hydrogen is improved; (4) preferably, as shown in fig. 3, the invention adopts a device for separating and purifying hydrogen by adopting a liquid organic carrier, wherein the device mainly comprises a closed tank body I, a cooling device I, a heating device I and a gas dispersing device I; the top of the closed tank body I is provided with a gas outlet, the closed tank body I is internally provided with a liquid organic matter carrier, the cooling equipment I and the heating equipment I are arranged in the liquid organic matter carrier in the closed tank body I, the gas dispersing equipment I is arranged in the liquid organic matter carrier in the closed tank body I, and the gas dispersing equipment I is connected and communicated with the outlet of the compressor I through a hydrogen-rich combustible gas pipeline;
The fuel gas storage tank belongs to a fuel gas storage tank for petrochemical industry;
the hydrogen storage equipment is one of the following equipment: (1) the high-pressure gas storage device adopts a compressor to convey 99.99 percent (wt%) hydrogen released in the 6 hydrogen separation and purification device into a steel bottle for storage and standby, (2) a liquefied hydrogen storage device, (3) a metal hydride storage device, (4) a physical adsorption hydrogen storage device, (5) preferably, the invention utilizes a device for storing hydrogen by using a liquid organic matter carrier, as shown in fig. 4, namely a compressor II is used to convey 99.99 percent (wt%) hydrogen released in the 6 hydrogen separation and purification device into the device for storing hydrogen by using the liquid organic matter carrier through a hydrogen pipeline for hydrogen absorption and storage; the device for storing hydrogen by the liquid organic matter carrier mainly comprises a closed tank body II, a cooling device II, a heating device II and a gas dispersing device II; the top of the second closed tank body is provided with a hydrogen outlet, and the second closed tank body is internally provided with a liquid organic carrier; the second cooling device and the second heating device are arranged in a liquid organic matter carrier in the second closed tank body, the second gas dispersing device is arranged in the liquid organic matter carrier in the second closed tank body, and the second gas dispersing device is connected and communicated with the second outlet of the compressor through a hydrogen pipeline;
The shell-and-tube condenser; belongs to a shell-and-tube heat exchanger adopted by the petrochemical industry;
further, the device adopts a method for preparing hydrogen from household garbage and/or organic matters, and comprises the following steps:
(1) Pretreatment: manually sorting household garbage and/or organic matters, breaking bags, removing iron by a magnetic separator, sieving or sorting to remove stone sediment, extruding, dehydrating or drying to obtain pretreated combustible matters;
(2) Pyrolysis gasification: loading the combustible material in the step (1) into a pyrolysis gasification furnace through a feeder for pyrolysis gasification; one of the following two methods is pyrolysis gasification under the condition of isolating oxygen, wherein the known catalyst is adopted for pyrolysis gasification or catalyst-free pyrolysis gasification, gas phase products and carbon residue are obtained after the pyrolysis gasification, and combustible gas generated by the pyrolysis gasification is led out of a pyrolysis gasification furnace to discharge the carbon residue; the other is to use air (or oxygen) as gasifying agent, to make pyrolysis vaporization by using vertical pyrolysis vaporization furnace, to obtain gas phase product and slag after pyrolysis gasification, to lead the gas phase product generated by pyrolysis gasification out of the pyrolysis vaporization furnace, and to discharge slag from the pyrolysis vaporization furnace;
(3) High-temperature cracking: introducing the gas phase product generated by pyrolysis and gasification in the step (2) into a high-temperature cracking furnace for anaerobic high-temperature cracking at 1000-1300 ℃, or conveying organic liquid and organic gas into the high-temperature cracking furnace for anaerobic high-temperature cracking at 1000-1300 ℃; the method comprises the steps of heating a high-temperature cracking furnace by adopting an indirect heat supply principle in a radiation heat transfer and convection heat transfer mode, introducing a proper amount of water vapor, directly triggering raw water gas reaction by the water vapor and a gas phase product, cracking and dehydrogenating a gas phase product generated by pyrolysis and gasification through high-temperature cracking, removing carbon residues generated by high-temperature cracking through the water gas reaction of the water vapor to obtain high-temperature combustible gas, and leading the combustible gas out of the high-temperature cracking furnace;
(4) Cooling and desulfurizing: cooling the high-temperature combustible gas discharged in the step (3) by adopting water in a waste heat steam boiler to absorb heat to generate steam, or cooling by adopting a mode of preheating the gas phase product in the step (2), and then performing desulfurization treatment on the combustible gas;
(5) And (3) hydrogen production by conversion: delivering the desulfurized combustible gas in the step (4) into shift hydrogen production equipment, introducing a proper amount of steam, carrying out shift reaction on carbon monoxide in the combustible gas and the steam under the action of a shift catalyst to produce hydrogen and carbon dioxide, obtaining hydrogen-rich combustible gas, and leading the hydrogen-rich combustible gas produced after the shift reaction out of the shift hydrogen production equipment;
(6) Condensing, separating and purifying hydrogen-rich fuel gas: the hydrogen-rich combustible gas led out of the hydrogen production equipment (5) is conveyed to gas-liquid separation equipment for gas-liquid separation after heat exchange to room temperature by a condenser, the hydrogen-rich combustible gas discharged from the gas-liquid separation equipment is led into gas purification equipment for purification treatment to remove carbon dioxide in the hydrogen-rich combustible gas, the purified hydrogen-rich combustible gas is led out of the gas purification equipment, liquid in the gas-liquid separation equipment is discharged from a liquid outlet at the lower part of the gas-liquid separation equipment, and the discharged liquid is collected and treated;
(7) And (3) hydrogen purification: introducing the purified hydrogen-rich combustible gas in the step (6) into hydrogen separation and purification equipment, and selecting one of the following methods to separate and purify hydrogen: (1) purifying hydrogen by membrane separation, (2) purifying hydrogen by PSA pressure swing adsorption gas separation, and (9) extracting hydrogen by PSA, and then performing membrane separation on tail gas after PSA process to extract residual hydrogen in tail gas after PAS; after membrane separation or PSA separation, 99.99% (wt%) pure hydrogen and other combustible gases are obtained, and the 99.99% (wt%) pure hydrogen and other combustible gases are respectively discharged from the hydrogen separation and purification equipment; (4) preferably, the technology of 'liquid organic matter carrier' for selectively absorbing and storing hydrogen is adopted to separate and purify hydrogen, see the third figure, wherein the 'liquid organic matter carrier' for selectively absorbing and storing hydrogen belongs to a composite liquid organic matter carrier; the purified hydrogen-rich combustible gas of the step 6 is input into a closed tank body I filled with a liquid organic matter carrier through a compressor I and a hydrogen-rich gas pipeline, hydrogen in the hydrogen-rich combustible gas is absorbed by the liquid organic matter carrier and is continuously stored in the closed tank body I, and other combustible gases cannot be absorbed and stored by the liquid organic matter carrier and are continuously discharged from the closed tank body I and are conveyed into a gas storage tank for storage; a first cooling device is arranged in the first closed tank body, and the cooling medium (such as cold water) flowing in the first cooling device is used for cooling the heat released in the process of absorbing the hydrogen; the hydrogen release belongs to endothermic reaction, heating is carried out in the hydrogen release process by utilizing a heating medium (such as heat conducting oil) flowing in a heating device I arranged in a closed tank body I, 99.99% (wt%) of hydrogen is released from a liquid organic matter carrier, and is released and discharged from the closed tank body I;
(8) Hydrogen storage: hydrogen storage was performed by one of three methods: (1) a compressor is adopted to convey the hydrogen released in the hydrogen separation and purification equipment (7) into a steel bottle for storage for standby; (2) storing hydrogen by adopting a liquid organic matter carrier; a second compressor is used for conveying 99.99 percent (wt%) hydrogen released in the hydrogen separation and purification equipment (7) into a second closed tank body filled with a liquid organic carrier for absorption and storage, the absorption and storage of hydrogen belongs to exothermic reaction, and the cooling is favorable for the absorption and storage of hydrogen; the heat released in the process of absorbing the hydrogen is cooled by using a cooling medium flowing in cooling equipment II in the closed tank body II; releasing hydrogen, heating the liquid organic matter carrier by using a heating device II arranged in the closed tank II to overflow the hydrogen adsorbed and stored in the liquid organic matter carrier, releasing the hydrogen from a hydrogen outlet of the closed tank II, and collecting and utilizing the released hydrogen;
in the two steps of (7) hydrogen purification and (8) hydrogen storage, the technical principles of hydrogen purification and hydrogen storage are as follows: by means of the principle that hydrogen can be absorbed and stored by the selected 'liquid organic matter carrier', and other fuel gas cannot be absorbed and stored by the selected 'liquid organic matter carrier', after the hydrogen and other gases enter the selected 'liquid organic matter carrier', the hydrogen is absorbed and stored by the selected 'liquid organic matter carrier', and the other gases cannot be absorbed, overflow from the selected 'liquid organic matter carrier', so that the hydrogen and the other gases are separated; in particular, the absorption and storage of hydrogen and the release of hydrogen by the selected "liquid organic carrier" are a pair of reversible reactions; the absorption and storage of hydrogen are exothermic processes, the low temperature is favorable for absorption and storage of hydrogen, and heat generated during absorption and storage of hydrogen is removed through cooling equipment in a liquid organic carrier; the hydrogen release is an endothermic process, which is carried out through endothermic catalytic dehydrogenation reaction, and the indirect heating of the liquid organic carrier is beneficial to the hydrogen release; when hydrogen is released, the liquid organic matter carrier is indirectly heated by a heating device I arranged in the closed tank I, and after the liquid organic matter carrier is heated, 99.99 percent (wt%) pure hydrogen is released from the hydrogen separation and purification device;
The invention discloses a liquid organic matter carrier capable of selectively absorbing and storing hydrogen, which belongs to a composite liquid organic matter carrier, and comprises a carrier body, a carrier body and a carrier body, wherein the carrier body is composed of a carrier body and a carrier body, the carrier body is composed of a carrier body, the carrier body and a carrier body, and the carrier body is composed of a carrier body and a carrier body. The petroleum ether (boiling range 90-120 ℃) accounts for 30% (wt%) and the mass hydrogen storage density thereof is 9.4% (wt%), the amyl alcohol accounts for 70% (wt%) and the mass hydrogen storage density thereof is 6.8% (wt%), the petroleum ether and the amyl alcohol with the weight proportion are uniformly mixed to prepare the composite liquid organic matter carrier, and the mass hydrogen storage density of the composite liquid organic matter carrier reaches 12.5% (wt%), so that the co-effect of increasing the mass hydrogen storage density (wt%) is generated, and the mass hydrogen storage density is improved;
the household garbage and/or organic matters comprise: kitchen waste, agriculture and forestry pasturage organic waste, industrial organic waste, straw, methanol, methane, fuel oil, coal tar, sludge, oil extraction plant oil sludge, oil sand, chinese honeylocust, animal and vegetable oil and landfill organic waste;
generally, the household garbage contains waste plastics, waste rubber, nylon, leather, organic polymer synthetic materials and other hydrocarbon wastes composed of carbon (C) and hydrogen (H) binary elements, and also contains straw, agriculture and forestry organic wastes (namely branches, leaves, grass and roots), paper scraps, ropes, cotton cloth, wood dust, livestock and poultry feathers, chinese honeylocust, waste grease, kitchen waste, animal waste and other biomass wastes composed of carbon (C), hydrogen (H) and oxygen (O) ternary elements; the raw materials for preparing hydrogen by organic matters also comprise: methanol, methane, gasoline, diesel, heavy oil, mined petroleum and other hydrocarbon substances;
In the pyrolysis gasification of the household garbage and/or the organic matters, hydrocarbon substances (such as waste plastics, waste rubber, fuel oil, oil sand and oil extraction plant oil sludge) are subjected to carbonization or pyrolysis gasification, and micromolecular hydrocarbon gas-phase products and carbon residues are obtained after pyrolysis gasification: hydrocarbon substances such as waste plastics (PP, PE, PS, PVC) and waste rubber (NR, SR, SBR, CR, NBR, EPM) are pyrolyzed under the condition of isolating air:
N[C+H 2 +CH 4 +C 2 H 4 +C 2 H 6 +C 3 H 6 +C 3 H 8 +C 4 H 10 +.......C 30 H 62 ]wherein C is a solid carbon residue product after air-isolated pyrolysis gasification, CH 4 -C 5 H 12 Is non-condensable combustible gas, C 6 H 14 -C 9 H 20 Is a gasoline component, C 10 H 14 -C 8 H 18 Is kerosene component, C 11 H 24 -C 20 H 42 Is a diesel oil component, C 21 H 44 -C 30 H 62 Is a heavy oil component;
the household garbage andand/or pyrolysis and gasification of organic matters, wherein biomass (such as branch, leaf, grass, root, paper scraps, rope, cotton cloth, wood scraps, animal feces, livestock and fowl hair, animal and vegetable oil and kitchen garbage) is subjected to pyrolysis and gasification to obtain wood gas (including CH) 4 、CO、CO 2 、H 2 、C 2 H 6 、C 2 H 4 ) Gas phase products and char residues of wood tar component and wood acetic acid component:
hydrocarbon material and gas phase product (including CH) after pyrolysis gasification of biomass 4 、CO、CO 2 、H 2 、C 2 H 6 、C 2 H 4 Wood gas, wood tar component, wood acetic acid component and C 2 H 6 -C 30 H 62 Hydrocarbon gas) is directly conveyed into a pyrolysis furnace to carry out anaerobic pyrolysis at 1000-1300 ℃, or liquid organic matters (such as methanol, gasoline, diesel oil, heavy oil, fuel oil and other liquid hydrocarbon matters of mined petroleum) and gaseous organic matters (such as methane) are conveyed into the pyrolysis furnace to carry out anaerobic pyrolysis at 1000-1300 ℃, a proper amount of water vapor is introduced, and indirect heat supply radiation heat transfer and convection heat transfer are adopted to carry out carbon chain fracture and hydrogen production reaction:
Carbon residue is generated in high-temperature pyrolysis, and reacts with steam to generate water gas to prepare hydrogen, so that the blockage of the carbon residue on equipment pipelines in the high-temperature pyrolysis is eliminated, the carbon residue is converted into hydrogen, and the yield of the hydrogen is improved;
the conversion rate of hydrogen is improved through a shift reaction, steam is introduced into a gas phase product after high-temperature pyrolysis containing carbon monoxide (CO), and CO and H generated in the high-temperature pyrolysis are produced through a shift hydrogen production reaction 2 O (g) is subjected to a shift reaction under the action of a shift catalyst to generate hydrogen (H) 2 ) And carbon dioxide (CO) 2 )：
CO+H 2 O(g)＝H 2 +CO 2
Carbon dioxide generated in the shift reaction is removed in the gas purifying apparatus of the above 6:
2NaOH+CO 2 ＝H 2 O+Na 2 CO 3
the invention directly conveys the gas phase products after pyrolysis gasification of garbage into a high-temperature pyrolysis furnace for high-temperature anaerobic pyrolysis at 1000-1300 ℃, directly cracks macromolecular hydrocarbon gas phase products, wood tar and wood acetic acid gas phase products into hydrogen and residual carbon, introduces water vapor, and contacts the residual carbon with the water vapor to generate water gas reaction so as to generate hydrogen-rich combustible gas which does not contain biomass tar and wood acetic acid, thereby improving the conversion rate of the hydrogen, and inhibiting and overcoming the blockage of the equipment pipeline by the residual carbon generated by the high-temperature pyrolysis, which is one of the inventive characteristics of the invention;
The invention adopts the technology of absorbing and storing hydrogen and releasing hydrogen by adopting a liquid organic carrier for selectively absorbing and storing hydrogen, which is a technology for separating high-purity hydrogen with 99.99 percent at low cost; the organic hydride is used for hydrogenation/dehydrogenation reaction under the conditions of increasing temperature and changing pressure and the reaction of a catalyst, the hydrogen storage and transportation volume and weight are also liquid at normal temperature and normal pressure, the hydrogen storage and transportation volume and weight are more advantageous than those of a common high-pressure hydrogen storage and metal hydrogen storage tank, the hydrogen storage agent (namely a liquid organic matter carrier) is low in cost and can be recycled for a plurality of times, a large amount of storage and long-distance transportation are facilitated, in the mode, hydrogen can not escape from hydrogen storage equipment, the safety is greatly improved, the hydrogen and hydrogen in a storage layer are purified and separated under normal pressure, and the purity of the purified hydrogen is more than 99.99% (wt%); the invention adopts the composite liquid organic matter carrier technology to purify hydrogen and store hydrogen, the mass hydrogen storage rate reaches 12.5 percent (wt%), the weight storage density of hydrogen is improved, and the invention is a second inventive feature;
the beneficial effects of the invention are as follows:
1. the gas phase products of the solid combustible substances in the household garbage after pyrolysis and gasification are directly conveyed into a high-temperature cracking furnace, or organic substances (such as methanol, methane, fuel oil and waste grease) are conveyed into the high-temperature cracking furnace, high-temperature cracking is carried out at 1000-1300 ℃ under the action of water vapor, and the high-temperature cracking directly cracks the organic substances (such as wood tar, wood acetic acid, methanol, methane, fuel oil and waste grease) into hydrogen and carbon residue, so that the hydrogen conversion rate is high, tar-free blocking equipment is not provided, the process flow is short, the operation cost is low, the heat utilization rate is high, and the popularization and application prospect is good;
2. The steam is introduced in the high-temperature pyrolysis, and the steam reacts with the carbon residue generated in the high-temperature pyrolysis to generate hydrogen, so that the conversion rate of the hydrogen is improved, and the blockage of the carbon residue generated in the high-temperature pyrolysis to the equipment pipeline is restrained and overcome;
3. the composite liquid organic matter carrier technology of the invention is used for purifying hydrogen and storing hydrogen, and is a low-cost normal-pressure hydrogen purification, in particular, the composite liquid organic matter carrier of the invention has the hydrogen storage weight density reaching 12.5% (wt%) and large hydrogen storage weight density, the purified hydrogen purity being more than 99.99% (wt%) and the hydrogen storage tank body being changeable, the hydrogen storage tank body being convenient to be configured on a transportation vehicle for use, and the invention is operated at normal pressure, safe and reliable, and has creative, novel and advanced industrial practicability.
Drawings
FIG. 1 is a schematic flow diagram of the process of the present invention;
FIG. 2 is a schematic diagram of an apparatus for carrying out the method of the present invention;
FIG. 3 is a schematic diagram of the apparatus for separating and purifying hydrogen by using the liquid organic matter carrier of the present invention;
FIG. 4 is a schematic diagram of the apparatus for storing hydrogen using a "liquid organic carrier" according to the present invention;
in FIGS. 1, 2, 3 and 4, 1-pretreatment apparatus, 2-feeder, 3-pyrolysis gasification furnace, 4-pyrolysis furnace, 5-waste heat steam boiler, 6-shift hydrogen production apparatus, 7-shift catalyst, 8-gas-liquid separation apparatus, 9-gas dispersion apparatus II, 10-gas purification apparatus, 11-hydrogen separation purification apparatus, 12-heating furnace, 13-gas storage tank, 14-hydrogen storage apparatus, 15-steam pipe I, 16-steam pipe II, 17-condenser, 18-liquid collection apparatus, 19-heating cracking pipe, 20-desulfurization apparatus, the device comprises a first pipeline, a first 22-compressor, a first 23-gas pipeline, a second 24-other gas outlet, a first 25-gas dispersing device, a first 26-liquid organic matter carrier, a first 27-cooling device, a first 28-hydrogen-rich gas pipeline, a first 29-heating device, a first 30-closed tank, a second 31-closed tank, a second 32-compressor, a second 33-hydrogen outlet, a 34-hydrogen pipeline, a second 35-pipeline, a second 36-cooling device, a second 37-heating device, a 38-organic liquid or organic gas storage tank, a 39-delivery pump, a first 40-valve and a second 41-valve;
Detailed Description
The invention is further described below with reference to the drawings and the detailed description, without however being limited thereto.
As shown in fig. 1, 2, 3 and 4, the device for preparing hydrogen from household garbage and/or organic matters mainly comprises a pretreatment device (1), a feeder (2), a pyrolysis gasification furnace (3), a high-temperature pyrolysis furnace (4), a waste heat steam boiler (5), a desulfurization device (20), a conversion hydrogen production device (6), a gas-liquid separation device (8), a light oil storage tank (9), a gas purification device (10), a hydrogen separation and purification device (11), a heating furnace (12), a gas storage tank (13), a first compressor (22), a second compressor (32), a hydrogen storage device (14), a condenser (17), a storage tank (38) of organic liquid or organic gas, a delivery pump (39), a first valve (40) and a second valve (41);
the pretreatment equipment (1) is utilized to connect and communicate the combustible materials separated from the household garbage and/or the organic matters with the inlet of a feeding machine (2) of a pyrolysis gasification furnace (2) through a conveying system, the gas phase product outlet of the pyrolysis gasification furnace (2) is connected and communicated with the inlet of a valve II (41), the discharge port of an organic liquid or organic gas storage tank (38) is connected and communicated with the inlet of a conveying pump (39) through a pipeline, the outlet of the conveying pump (39) is connected and communicated with the inlet of a valve I (40) through a pipeline, the outlet of the valve I (40) and the outlet of the valve II (41) are respectively connected and communicated with the inlet of a heating cracking tube (19) in a high-temperature pyrolysis furnace (4) through a pipeline, the outlet of the heating cracking tube (19) in the high-temperature pyrolysis furnace (4) is connected and communicated with the inlet of a flue gas heating chamber of a waste heat steam boiler (5) through a pipeline, the outlet of the flue gas heating chamber of the waste heat steam boiler (5) is connected and communicated with the inlet of a desulfurization equipment (20) through a pipeline, the outlet of the desulfurization equipment (20) is connected and communicated with the inlet of a conversion equipment (6) through a pipeline, the outlet of the waste heat boiler (5) is respectively communicated with the inlet of the heating tube (21) and the steam boiler (15) in the high-temperature pyrolysis gasification furnace (4) is communicated with the steam boiler (7) through the steam inlet of the waste heat boiler (7) through the conversion equipment (7), the conversion hydrogen production equipment (6) belongs to a fixed bed structure, a solid conversion catalyst (7) is arranged on a sieve plate in the middle of the conversion hydrogen production equipment (6), a discharge hole in the lower part of the conversion hydrogen production equipment (6) is connected and communicated with a material inlet of a condenser (17) through a pipeline, a material outlet of the condenser (17) is connected and communicated with an inlet of a gas-liquid separation equipment (8) through a pipeline, a gas phase outlet in the upper part of the gas-liquid separation equipment (8) is connected and communicated with a gas inlet of a gas purification equipment (10) through a pipeline II (35), and a liquid outlet is arranged at the bottom of the gas-liquid separation equipment (8) and is connected and communicated with an inlet of a liquid collecting equipment (18) through a pipeline; the outlet of the gas purifying device (10) is communicated with the air inlet of the first compressor (22) through a pipeline, the air outlet of the first compressor (22) is communicated with the inlet of the hydrogen separating and purifying device (11) through a pipeline, the pure hydrogen outlet of the hydrogen separating and purifying device (11) is communicated with the inlet of the second compressor (32) through a pipeline, the outlet of the second compressor (32) is communicated with the air inlet of the hydrogen storage device (14) through a pipeline through a hydrogen pipeline (34), and the other gas outlets of the hydrogen separating and purifying device (11) are communicated with the inlet of the gas storage tank (13) through a gas pipeline (23); the outlet of the fuel gas storage tank (13) is connected and communicated with the fuel inlet of the heating furnace (12) through a pipeline; the flue gas outlet after the combustion of the heating furnace (12) is connected and communicated with the inlet of the heating chamber of the high-temperature cracking furnace (4) through a flue built by a high-temperature weather-resistant material;
The pretreatment equipment (1) comprises a garbage grab bucket machine, a bag breaking machine, a sorting machine, a magnetic separator and a dryer, wherein household garbage and/or organic matters are manually sorted, the grab bucket machine is used for feeding, bag breaking and iron and soil separation are carried out, organic garbage is obtained, and pretreated garbage materials are obtained after the organic garbage is dried;
the feeder (2) belongs to a hydraulic reciprocating feeder, a screw conveyor or other garbage feeders;
the pyrolysis gasification furnace (3) belongs to an anaerobic pyrolysis gasification furnace or a vertical pyrolysis gasification furnace which uses air (oxygen) as a gasifying agent; a vertical pyrolysis gasification furnace adopting air (oxygen) as gasifying agent, comprising a fixed bed gasification furnace, a fluidized bed gasification furnace and an air flow bed gasification furnace, preferably a fixed bed gasification furnace, wherein the fixed bed gasification furnace is divided into a drying zone, a pyrolysis zone, a combustion zone, a slag discharging zone at the lower part and a slag discharging zone at the upper part; the garbage materials enter a gasification furnace and then are dried, then enter a pyrolysis zone to generate gas-phase products, a combustion zone provides energy for the whole system, and the pyrolyzed carbon residues are fully mixed with gasifying agents (air and oxygen) fed by a nozzle and are vigorously combusted to generate water, carbon trioxide and the like, and heat is released; separating small-particle ash, slag or tar from a gas-phase product discharged from the gasification furnace through a cyclone separator, then entering a next high-temperature cracking furnace for cracking, and discharging inorganic slag from the lower part of the gasification furnace;
The high-temperature cracking furnace (4) belongs to a high-temperature cracking tube furnace in an anaerobic environment, adopts an indirect heat supply principle, and utilizes a radiation heat transfer and convection heat transfer heating mode to heat materials in a heating cracking tube (19); under the condition of isolating air, the material is subjected to carbon chain fracture or dehydrogenation under the action of high temperature; the main structure comprises: the device comprises a radiation chamber, a convection chamber, a waste heat recovery system, a burner and a ventilation system;
the heating furnace (12) belongs to a device for heating the high-temperature cracking furnace in petrochemical industry, and can adopt gas heating, fuel oil heating and high-temperature plasma flame heating;
the waste heat steam boiler (5) belongs to a tubular steam generator;
the desulfurization equipment (20) belongs to gas desulfurization equipment in petrochemical industry;
the shift hydrogen production equipment (6) belongs to equipment for generating hydrogen and carbon dioxide under the action of a shift catalyst (7) in a fixed bed by carbon monoxide and water vapor, such as equipment for producing hydrogen by carbon monoxide shift in the ammonia synthesis industry;
the gas-liquid separation equipment (8) belongs to gas-phase and liquid-phase separation equipment used in petrochemical industry, the gas is discharged from the upper part of the equipment, and the liquid phase (such as oil and water) is discharged from a side wall pipe orifice valve at the lower part of the equipment;
The liquid collecting device (18) belongs to an oil-water collecting and buffering tank in petrochemical industry;
the gas purifying device (10) belongs to the gas purifying device in petrochemical industry, has the functions of desulfurization, dechlorination, tar removal and dust removal, and comprises an alkaline washing tower, wherein alkali liquor is used for reacting with acidic substances (such as sulfur dioxide, hydrogen sulfide, hydrogen chloride and carbon dioxide) in the gas to remove the acidic substances in the gas, and liquid is used for washing dust in the gas;
the gas storage tank (13) belongs to a gas storage tank for petrochemical industry;
the hydrogen separation and purification device (11) is one of the following devices: (1) the hydrogen is extracted by adopting a single membrane separation device, (2) the hydrogen is extracted by adopting a single PSA pressure swing adsorption gas separation device, (3) the hydrogen is extracted by adopting a PSA device, and then the tail gas after the hydrogen is extracted by the PSA device is subjected to a further recovery device of the hydrogen extracted by the membrane separation device, so that the recovery rate of the hydrogen is improved; (4) optionally, as shown in fig. 3, the invention adopts a device for separating and purifying hydrogen by adopting a liquid organic carrier, wherein the device mainly comprises a closed tank body I (30), a cooling device I (27), a heating device I (29) and a gas dispersing device I (25); a gas outlet (24) is arranged at the top of the first closed tank body (30), a liquid organic matter carrier (26) is arranged in the first closed tank body (30), a cooling device I (27) and a heating device I (29) are arranged in the liquid organic matter carrier (26) in the first closed tank body (30), a gas dispersing device I (25) is arranged in the liquid organic matter carrier (26) in the first closed tank body (30), and the gas dispersing device I (25) is communicated with the outlet of the first compressor (22) through a hydrogen-rich combustible gas pipeline (29);
The hydrogen storage device (14) is one of the following devices: (1) the high-pressure gas storage device adopts a compressor to convey 99.99 percent (wt%) hydrogen released in the 6 hydrogen separation and purification device into a steel bottle for storage and standby, (2) a liquefied hydrogen storage device, (3) a metal hydride storage device, (4) a physical adsorption hydrogen storage device, (5) preferably, the invention utilizes a device for storing hydrogen by using a liquid organic matter carrier, as shown in fig. 4, namely a compressor II (32), and conveys 99.99 percent (wt%) hydrogen released in the 6 hydrogen separation and purification device (11) into a liquid organic matter carrier (26) of the invention through a hydrogen pipeline (34) for hydrogen absorption and storage; the hydrogen storage equipment for the liquid organic matter carrier mainly comprises a closed tank body II (31), a cooling device II (36), a heating device II (37) and a gas dispersing device II (9); a hydrogen outlet (33) is arranged at the top of the second closed tank body (31), and a liquid organic carrier (26) is arranged in the second closed tank body (31); the second cooling device (36) and the second heating device (37) are arranged in a liquid organic matter carrier (26) in the second closed tank body (31), the second gas dispersing device (9) is arranged in the liquid organic matter carrier (26) in the second closed tank body (31), and the second gas dispersing device (9) is connected and communicated with an outlet of the second compressor (32) through a hydrogen pipeline (34);
The technical principle of the method for preparing hydrogen by utilizing the device to implement the domestic garbage and/or organic matters is as follows:
(1) Pyrolysis gasification of household garbage and/or organic matters is a process of utilizing thermal instability of the organic matters to break compound bonds of the compounds under anaerobic or aerobic conditions by utilizing thermal energy, and converting the organic matters with large molecular weight into combustible gas, liquid, fuel and carbon residue with small molecular weight;
(2) The high-temperature pyrolysis is a process of deeply thermally cracking a gas-phase product after pyrolysis and gasification or an organic liquid into hydrogen (H2) and carbon (C) at a high temperature of 1000-1300 ℃, carbon residue generated in pyrolysis and gasification are contacted with high-temperature steam to generate water gas for reaction to generate hydrogen and carbon dioxide, so that the conversion rate of the hydrogen is improved, and the blockage of the carbon residue generated by high-temperature pyrolysis on equipment pipelines is restrained and overcome;
(3) The shift hydrogen production is to shift the carbon monoxide in the gas phase product after pyrolysis gasification and high temperature pyrolysis to produce hydrogen and carbon dioxide, and the high temperature steam and the carbon monoxide are subjected to shift reaction under the action of a shift catalyst to produce hydrogen and carbon dioxide; the hydrogen conversion rate of garbage hydrogen production is improved;
(4) The hydrogen separation and purification method adopts the following steps: (1) adopting a membrane separation technology, (2) adopting a PSA pressure swing adsorption gas separation and purification hydrogen technology, (3) adopting a technology of firstly carrying out PSA to extract hydrogen, then carrying out membrane separation on tail gas after the PSA process, extracting residual hydrogen in the tail gas after PAS, and obtaining 99.99% (wt%) pure hydrogen and other combustible gases after membrane separation or PSA separation; (4) the technology for purifying hydrogen by adopting a liquid organic matter carrier adopts the following principle: by means of the principle that hydrogen can be absorbed and stored by the selected 'liquid organic matter carrier', and other fuel gas cannot be absorbed and stored by the selected 'liquid organic matter carrier', after the hydrogen and other gases enter the selected 'liquid organic matter carrier', the hydrogen is absorbed and stored by the selected 'liquid organic matter carrier', and the other gases cannot be absorbed, overflow from the selected 'liquid organic matter carrier', so that the hydrogen and the other gases are separated; the hydrogen absorption and the hydrogen release are realized by virtue of a pair of reversible reactions of a liquid organic matter carrier selectively absorbing hydrogen and hydrogen, the hydrogen absorption is an exothermic process, the hydrogen release is an endothermic process, and after the liquid organic matter carrier is heated, 99.99 percent (wt%) pure hydrogen is released from a hydrogen separation and purification device;
(5) Hydrogen storage: (1) the hydrogen released in the hydrogen separation and purification equipment is conveyed to a steel bottle for storage by adopting hydrogen compression equipment, (2) the hydrogen is conveyed to a closed tank body II loaded with a liquid organic matter carrier for storage by adopting a compressor II, and the hydrogen is absorbed and stored by virtue of the principle that the hydrogen can be absorbed and stored by the selected liquid organic matter carrier, but other fuel gas cannot be absorbed and stored by the selected liquid organic matter carrier, and when the hydrogen and other gases enter the selected liquid organic matter carrier at the same time, the hydrogen is absorbed and stored by the selected liquid organic matter carrier; the absorption and storage of hydrogen by the liquid organic matter carrier are carried out through exothermic catalytic hydrogenation reaction, the release of hydrogen is carried out through endothermic catalytic dehydrogenation reaction, and when the liquid organic matter carrier in the sealed tank II is heated, the hydrogen with the purity of more than 99.99% (wt%) is released for utilization, and the released hydrogen is collected and utilized;
example one domestic waste Hydrogen production
The method for preparing hydrogen by using domestic garbage as raw material, see fig. 1, 2, 3 and 4, comprises the following steps:
1. pretreatment: manually sorting the household garbage, then conveying the household garbage into pretreatment equipment (1) for bag breaking, iron removal by a magnetic separator, screening or sorting to remove stone sediment, extruding and dehydrating or drying to obtain pretreated combustible materials;
2. Pyrolysis gasification: the combustible material in the step 1 is filled into a vertical pyrolysis gasification furnace which adopts air as a gasifying agent to carry out pyrolysis gasification by using a feeder (2), the combustible material passes through a drying zone, a pyrolysis zone, a combustion zone and a reduction zone in the vertical pyrolysis gasification furnace, the combustion zone provides energy for the whole system, the pyrolyzed residual carbon is fully mixed with the injected gasifying agent (air) to generate violent combustion to generate water, carbon dioxide and the like, the heat is released, furnace slag generated by pyrolysis gasification is discharged from the bottom of the pyrolysis gasification furnace, gas phase products generated by the pyrolysis zone are discharged from the pyrolysis gasification furnace, small particle ash, slag or tar is separated by a cyclone separator, and then the furnace slag enters a next high-temperature pyrolysis furnace to carry out pyrolysis;
3. high-temperature cracking: closing a valve I (40), opening a gate valve II (41), introducing a gas phase product generated by pyrolysis and gasification of the gas phase product 2 into a high-temperature cracking furnace (4) through a pipeline I (21) to perform anaerobic high-temperature cracking, heating a heating cracking pipe (19) in the high-temperature cracking furnace (4) by using combustion of fuel gas in a heating furnace (12), and enabling the gas phase product flowing in the heating cracking pipe (19) to reach 1100-1300 ℃ to perform deep cracking of the gas phase product, wherein fuel gas stored in a fuel gas storage tank (13) supplies fuel to the heating furnace (12); the water vapor generated by the waste heat steam boiler (5) is conveyed into a pipeline I (21) through a steam pipeline I (15), and the water vapor and a gas-phase product discharged by the pyrolysis gasification furnace (3) are contacted and uniformly mixed in the pipeline I (21) and then enter a heating cracking pipe (19) in the high-temperature cracking furnace (4); the radiation heat transfer and convection heat transfer adopting an indirect heat supply principle are adopted, carbon chain fracture and dehydrogenation are carried out on gas phase products under the dual actions of high temperature and water vapor, carbon residue is removed, high-temperature combustible gas is obtained, water in a waste heat steam boiler (5) is adopted to absorb heat and produce steam for cooling, the gas phase products are preheated for heating or cooled by adopting cold water, the temperature of the high-temperature combustible gas is reduced to 180-500 ℃, and the cooled combustible gas is led out from a high-temperature cracking furnace (4);
4. Desulfurizing: delivering the combustible gas cooled to 180-500 ℃ in the desulfurization equipment (20), desulfurizing under the action of a catalyst, and discharging the desulfurized combustible gas from the desulfurization equipment (20);
5. and (3) preparing hydrogen by a shift reaction: delivering the fuel gas discharged after desulfurization into a shift hydrogen production device (6), delivering water vapor generated by a waste heat steam boiler (5) into the shift hydrogen production device (6) through a second steam pipeline (16), carrying out contact mixing on the water vapor and the fuel gas discharged by a desulfurization device (20) in the shift hydrogen production device (6), carrying out shift reaction on carbon monoxide and water vapor in a gas phase product under the action of a shift catalyst (7) to generate hydrogen and carbon dioxide, obtaining hydrogen-rich fuel gas, and leading the hydrogen-rich fuel gas generated after the shift reaction out of the shift hydrogen production device (6);
6. condensing, separating and purifying hydrogen-rich fuel gas: the hydrogen-rich combustible gas led out of the hydrogen production equipment (6) is conveyed to a gas-liquid separation equipment (8) for gas-liquid separation after heat exchange to room temperature by a condenser (17), the hydrogen-rich combustible gas discharged from the gas-liquid separation equipment (8) is led into a gas purification equipment (10) for purification treatment, sodium hydroxide solution is adopted to absorb acid gas (such as hydrogen sulfide, hydrogen chloride and carbon dioxide) and dust in the hydrogen-rich combustible gas, the purified hydrogen-rich combustible gas is led out of the gas-liquid separation equipment (8), and liquid in the gas-liquid separation equipment (8) is discharged from an outlet at the bottom of the gas-oil-liquid separation equipment (8) and enters a liquid collection equipment (18) for collection, treatment and utilization;
7. And (3) hydrogen purification: introducing the purified hydrogen-rich combustible gas into hydrogen separation and purification equipment (11), and separating and purifying hydrogen by adopting a technology of selectively absorbing a liquid organic matter carrier for storing hydrogen, wherein the technology is shown in fig. 3 and comprises the following two steps:
and (1) absorbing hydrogen by a liquid organic matter carrier: the purified hydrogen-rich combustible gas is input into a closed tank body I (30) provided with a liquid organic matter carrier (26) through a compressor I (22), a hydrogen-rich gas pipeline (28) and a gas dispersing device I (25), hydrogen in the hydrogen-rich combustible gas is absorbed by the liquid organic matter carrier (26) and is continuously absorbed and stored in the liquid organic matter carrier (26) in the closed tank body I (30), other combustible gases cannot be absorbed by the liquid organic matter carrier (26), and the purified hydrogen-rich combustible gas is continuously discharged from other gas outlets (24) above the closed tank body I (30) and is conveyed into a gas storage tank (13) to be stored for standby, or the gas in the gas storage tank (13) is conveyed into a heating furnace (12) to be burnt for supplying heat to a high-temperature cracking furnace (4); the hydrogen is absorbed by a liquid organic matter carrier (26) and belongs to exothermic reaction, and the heat generated by the exothermic reaction is removed by a cooling device I (27) in a closed tank body I (30) so as to separate the hydrogen from other combustible gases;
(II) the liquid organic matter carrier releases hydrogen: when hydrogen is released, the liquid organic matter carrier (26) is indirectly heated by a first heating device (29) arranged in a first closed container (30), and after the liquid organic matter carrier (26) is heated, 99.99 percent (wt%) of pure hydrogen is released from the hydrogen separation and purification device (11);
7. hydrogen storage: the second compressor (22) is used to convey 99.99% (wt%) hydrogen released from the above-mentioned 7. Hydrogen separation and purification device (11) into the second closed tank (31) loaded with the liquid organic carrier (26) for storage, as shown in fig. 4, the "liquid organic carrier" technology of selectively absorbing hydrogen for storage and releasing hydrogen is used to store hydrogen, and the method comprises the following two steps:
and (1) the liquid organic matter carrier (26) absorbs and stores hydrogen: the purified hydrogen is input into a closed tank body II (31) provided with the liquid organic matter carrier (26) through a compressor II (32), a hydrogen pipeline (34) and a gas dispersing device II (38), the hydrogen is absorbed by the liquid organic matter carrier (26) and is continuously absorbed and stored in the liquid organic matter carrier (26) in the closed tank body II (31), the absorption of the hydrogen belongs to exothermic reaction, the temperature of the liquid organic matter carrier (26) is reduced, the absorption and the storage of the hydrogen are facilitated, and the heat generated by the exothermic reaction is removed by a cooling device (36) in the closed tank body II (31);
(II) the liquid organic matter carrier releases hydrogen: when hydrogen is released, the liquid organic matter carrier (26) is indirectly heated through a second heating device (37) arranged in the second closed container (31), 99.99% (wt%) pure hydrogen is released from a hydrogen outlet (33) at the top of the second closed container (31) after the liquid organic matter carrier (26) is heated, and the released hydrogen is collected and utilized;
EXAMPLES preparation of Hydrogen from dimethanol
The method for preparing hydrogen by using methanol as a raw material, see fig. 1, 2, 3 and 4, comprises the following steps:
1. high-temperature cracking: closing a valve II (41), opening a valve I (40), conveying methanol stored in an organic liquid or organic gas storage tank (38) into a high-temperature cracking furnace (4) by using a conveying pump (39) to perform anaerobic high-temperature cracking, heating a heating cracking pipe (19) in the high-temperature cracking furnace (4) by using combustion of fuel gas in the heating furnace (12), and enabling a gas-phase product flowing in the heating cracking pipe (19) to reach 1100-1300 ℃ to perform deep cracking of the gas-phase product, wherein fuel gas stored in a fuel gas storage tank (13) is used for supplying fuel to the heating furnace (12); the water vapor generated by the waste heat steam boiler (5) is conveyed into a pipeline I (21) through a steam pipeline I (15), and the water vapor and a gas-phase product discharged by the pyrolysis gasification furnace (3) are contacted and uniformly mixed in the pipeline I (21) and then enter a heating cracking pipe (19) in the high-temperature cracking furnace (4); the radiation heat transfer and convection heat transfer adopting an indirect heat supply principle are adopted, carbon chain fracture and dehydrogenation are carried out on gas phase products under the dual actions of high temperature and water vapor, carbon residue is removed, high-temperature combustible gas is obtained, water in a waste heat steam boiler (5) is adopted to absorb heat and produce steam for cooling, the gas phase products are preheated for heating or cooled by adopting cold water, the temperature of the high-temperature combustible gas is reduced to 180-500 ℃, and the cooled combustible gas is led out from a high-temperature cracking furnace (4);
According to the same steps as those of the embodiment, the combustible gas led out from the pyrolysis furnace (4) is subjected to desulfurization, hydrogen production by conversion reaction, condensation separation and purification of hydrogen-rich fuel gas, hydrogen purification and hydrogen storage in sequence, 99.99% (wt%) pure hydrogen is released from a hydrogen outlet (33) at the top of the second closed container (31), and the released hydrogen is collected and utilized.
Examples preparation of Hydrogen from Trimethane (Natural gas)
The hydrogen is prepared by using methane (natural gas) as a raw material, and referring to fig. 1, 2, 3 and 4, the method comprises the following steps:
1. high-temperature cracking: closing a valve II (41), opening a valve I (40), conveying natural gas (methane) stored in an organic liquid or organic gas storage tank (38) into a high-temperature cracking furnace (4) by using a conveying pump (39) to perform anaerobic high-temperature cracking, heating a heating cracking pipe (19) in the high-temperature cracking furnace (4) by using combustion of fuel gas in the heating furnace (12), enabling a gas-phase product flowing in the heating cracking pipe (19) to reach 1100-1300 ℃ to perform deep cracking of the gas-phase product, and supplying fuel to the heating furnace (12) by using the fuel gas stored in a fuel gas storage tank (13); the water vapor generated by the waste heat steam boiler (5) is conveyed into a pipeline I (21) through a steam pipeline I (15), and the water vapor and a gas-phase product discharged by the pyrolysis gasification furnace (3) are contacted and uniformly mixed in the pipeline I (21) and then enter a heating cracking pipe (19) in the high-temperature cracking furnace (4); the radiation heat transfer and convection heat transfer adopting an indirect heat supply principle are adopted, carbon chain fracture and dehydrogenation are carried out on gas phase products under the dual actions of high temperature and water vapor, carbon residue is removed, high-temperature combustible gas is obtained, water in a waste heat steam boiler (5) is adopted to absorb heat and produce steam for cooling, the gas phase products are preheated for heating or cooled by adopting cold water, the temperature of the high-temperature combustible gas is reduced to 180-500 ℃, and the cooled combustible gas is led out from a high-temperature cracking furnace (4);
According to the same steps as those of the embodiment, the combustible gas led out from the pyrolysis furnace (4) is subjected to desulfurization, hydrogen production by conversion reaction, condensation separation and purification of hydrogen-rich fuel gas, hydrogen purification and hydrogen storage in sequence, 99.99% (wt%) pure hydrogen is released from a hydrogen outlet (33) at the top of the second closed container (31), and the released hydrogen is collected and utilized.
Example four production of Hydrogen from waste Plastic and waste tires
The hydrogen is prepared by using waste plastics and waste tires as raw materials, and referring to fig. 1, 2, 3 and 4, the method comprises the following steps:
1. pretreatment: crushing 50 percent (wt%) of waste plastics and 50 percent (wt%) of waste tires to 5-10 cm in size, and removing iron by a magnetic separator to obtain a pretreated combustible material;
2. pyrolysis gasification: opening a valve II (41), closing a valve I (40), filling the combustible material of the valve I (1) into a pyrolysis gasification furnace (3) isolated from oxygen through a feeder (2), indirectly heating high-temperature flue gas by combusting gas in a heating furnace (12) to the outer wall of the pyrolysis gasification furnace (3), controlling the pyrolysis temperature of the combustible material in the pyrolysis gasification furnace (3) to be 350-500 ℃, performing pyrolysis reaction on the combustible material after being heated to obtain gas-phase products and carbon residues, leading the gas-phase products out of the pyrolysis gasification furnace (3), and discharging the carbon residues from the pyrolysis gasification furnace (3);
3. High-temperature cracking: opening a valve II (41), closing a valve I (40), conveying a gas phase product discharged from the pyrolysis gasification furnace (3) of the step 2 into a high-temperature pyrolysis furnace (4) for anaerobic high-temperature pyrolysis, heating a heating cracking pipe (19) in the high-temperature pyrolysis furnace (4) by using combustion of fuel gas in a heating furnace (12) to enable the gas phase product flowing in the heating cracking pipe (19) to reach 1100-1300 ℃ for deep pyrolysis of the gas phase product, and supplying fuel to the heating furnace (12) by using fuel gas stored in a fuel gas storage tank (13); the water vapor generated by the waste heat steam boiler (5) is conveyed into a pipeline I (21) through a steam pipeline I (15), and the water vapor and a gas-phase product discharged by the pyrolysis gasification furnace (3) are contacted and uniformly mixed in the pipeline I (21) and then enter a heating cracking pipe (19) in the high-temperature cracking furnace (4); the radiation heat transfer and convection heat transfer adopting an indirect heat supply principle are adopted, carbon chain fracture and dehydrogenation are carried out on gas phase products under the dual actions of high temperature and water vapor, carbon residue is removed, high-temperature combustible gas is obtained, water in a waste heat steam boiler (5) is adopted to absorb heat and produce steam for cooling, the gas phase products are preheated for heating or cooled by adopting cold water, the temperature of the high-temperature combustible gas is reduced to 180-500 ℃, and the cooled combustible gas is led out from a high-temperature cracking furnace (4);
According to the same steps as those of the embodiment, the combustible gas led out from the pyrolysis furnace (4) is subjected to desulfurization, hydrogen production by conversion reaction, condensation separation and purification of hydrogen-rich fuel gas, hydrogen purification and hydrogen storage in sequence, 99.99% (wt%) pure hydrogen is released from a hydrogen outlet (33) at the top of the second closed container (31), and the released hydrogen is collected and utilized.
Example five straw and forestry and agricultural residues to prepare hydrogen
The method for preparing hydrogen by using straw and agricultural and forestry waste as raw materials, which refer to fig. 1, 2, 3 and 4, comprises the following steps:
1. pretreatment: crushing 40% (wt%) of straw, 25% (wt%) of waste branches in gardens and 35% (wt%) of leaves into 5-10 cm size, and drying to obtain pretreated combustible material;
2. pyrolysis gasification: the combustible material in the step 1 is filled into a vertical pyrolysis gasification furnace which adopts air as a gasifying agent to carry out pyrolysis gasification by using a feeder (2), the combustible material passes through a drying zone, a pyrolysis zone, a combustion zone and a reduction zone in the vertical pyrolysis gasification furnace, the combustion zone provides energy for the whole system, the pyrolyzed residual carbon is fully mixed with the injected gasifying agent (air) to generate severe combustion to generate water, carbon trioxide and the like, the heat is released, furnace slag generated by pyrolysis gasification is discharged from the bottom of the pyrolysis gasification furnace, gas phase products generated by the pyrolysis zone are discharged from the pyrolysis gasification furnace, small particle ash, slag or tar is separated by a cyclone separator, and then the furnace enters a next high-temperature pyrolysis furnace to carry out pyrolysis;
According to the same steps as the embodiment, the gas phase product discharged from the pyrolysis gasification is subjected to high-temperature pyrolysis, desulfurization, shift reaction hydrogen production, condensation separation and purification of hydrogen-rich gas in sequence, the hydrogen-rich gas discharged after the purification treatment is subjected to PSA pressure swing adsorption gas separation and purification of hydrogen to obtain 99.99% (wt%) pure hydrogen, and the 99.99% (wt%) pure hydrogen is compressed into a steel cylinder by a compressor for storage.
Example six sludge production of Hydrogen
The method for preparing hydrogen by using sludge as a raw material, see fig. 1, 2, 3 and 4, comprises the following steps:
1. pyrolysis gasification: opening a valve II (41), closing a valve I (40), feeding 83% (wt%) of sludge containing water into a horizontal pyrolysis gasification furnace (3) with an isolated oxygen belt stirrer through a screw conveyor (2), adopting combustion of gas in a heating furnace (12) to indirectly heat high-temperature flue gas to the outer wall of the pyrolysis gasification furnace (3), controlling the pyrolysis temperature of the sludge in the pyrolysis gasification furnace (3) to be 350-500 ℃, performing pyrolysis reaction on the sludge after the stirring action and heating to obtain gas products and carbon ash, leading the gas products out of the pyrolysis gasification furnace (3), and discharging residual ash and carbon from the pyrolysis gasification furnace (3);
2. High-temperature cracking: opening a valve II (41), closing a valve I (40), and conveying the gas products discharged from the pyrolysis gasification furnace (3) in the pyrolysis furnace (4) to perform anaerobic pyrolysis; according to the same steps as those of the embodiment, the gas products entering the high-temperature cracking furnace (4) are subjected to desulfurization, hydrogen production by conversion reaction, condensation separation and purification of hydrogen-rich gas, hydrogen purification and hydrogen storage in sequence, 99.99% (wt%) pure hydrogen is released from a hydrogen outlet (33) at the top of a second closed container (31), and the released hydrogen is collected and utilized.
Claims (4)
1. The device comprises pretreatment equipment, a feeder, a pyrolysis gasification furnace, a high-temperature pyrolysis furnace, a waste heat steam boiler, desulfurization equipment, conversion hydrogen production equipment, gas-liquid separation equipment, liquid collection equipment, gas purification equipment, hydrogen separation and purification equipment, a heating furnace, a gas storage tank, a compressor, hydrogen storage equipment, a condenser, an organic liquid or organic gas storage tank, a delivery pump, a valve I and a valve II; the method is characterized in that: the method comprises the steps that combustible materials selected from household garbage and/or organic matters are connected and communicated with a feeder inlet of a pyrolysis gasification furnace through a conveying system by utilizing pretreatment equipment, a gas-phase product outlet of the pyrolysis gasification furnace is connected and communicated with a valve II inlet, the valve II outlet is respectively connected and communicated with an outlet of a valve I and a heating cracking pipe inlet in a high-temperature pyrolysis furnace, a discharge port of an organic liquid or organic gas storage tank is connected and communicated with an inlet of a conveying pump through a pipeline, and an outlet of the conveying pump is connected and communicated with an inlet of the valve I through a pipeline; the heating cracking pipe outlet in the high-temperature cracking furnace is connected and communicated with the flue gas heating chamber inlet of the waste heat steam boiler through a first pipeline, the flue gas heating chamber outlet of the waste heat steam boiler is connected and communicated with the inlet of the gas-liquid separation device through a pipeline, the steam outlet of the waste heat steam boiler is connected and communicated with the pipeline through a first steam pipe, the steam outlet of the waste heat steam boiler is connected and communicated with the upper part of the conversion catalyst in the conversion hydrogen production device through a second steam pipe, the conversion hydrogen production device belongs to a fixed bed structure, the solid conversion catalyst is arranged on a sieve plate in the middle of the conversion hydrogen production device, the discharge port in the lower part of the conversion hydrogen production device is connected and communicated with the material inlet of the condenser through a pipeline, the material outlet of the condenser is connected and communicated with the inlet of the gas-liquid separation device through a pipeline, the gas outlet in the upper part of the gas-liquid separation device is connected and communicated with the gas inlet of the gas purification device through a second pipeline, and the bottom of the gas-liquid separation device is provided with the liquid outlet through a pipeline and communicated with the inlet of the liquid collection device; the outlet of the gas purifying device is communicated with the inlet of the first compressor through a pipeline, the outlet of the first compressor is communicated with the inlet of the hydrogen separating and purifying device through a pipeline, the outlet of pure hydrogen of the hydrogen separating and purifying device is communicated with the inlet of the second compressor through a pipeline, the outlet of the second compressor is communicated with the inlet of the hydrogen storage device through a pipeline, and the other gas outlets of the hydrogen separating and purifying device are communicated with the inlet of the gas storage tank through gas pipelines; the outlet of the fuel gas storage tank is communicated with the fuel inlet of the heating furnace through a pipeline; the flue gas outlet after combustion of the heating furnace is connected and communicated with the inlet of the heating chamber of the high-temperature cracking furnace through a flue built by high-temperature weather-resistant materials;
The pretreatment equipment comprises a garbage grab bucket machine, a bag breaking machine, a sorting machine, a magnetic separator and a dryer, belongs to a common garbage pretreatment device of a household garbage incineration power plant, and comprises the steps of feeding, bag breaking and sorting household garbage through the grab bucket machine to remove ironware and soil to obtain organic garbage, and drying the organic garbage to obtain pretreated combustible;
the feeding machine belongs to a hydraulic reciprocating feeding machine, a screw conveyor or a garbage feeding machine;
the organic liquid or organic gas storage tank belongs to a pressure-resistant steel fuel storage tank in petrochemical industry;
the conveying pump belongs to an explosion-proof gas conveying pump or a liquid conveying pump used in petrochemical industry;
the pyrolysis gasification furnace is one gasification furnace selected from (1) a vertical or horizontal anaerobic pyrolysis gasification furnace with a stirring device, and (2) a pyrolysis gasification furnace with air (or oxygen) as a gasifying agent; comprises a fixed bed gasification furnace, a fluidized bed gasification furnace and an air flow bed gasification furnace, preferably a fixed bed gasification furnace, wherein the fixed bed gasification furnace is divided into a drying zone, a pyrolysis zone, a combustion zone, a still wish zone and a lower slag discharging zone;
the high-temperature cracking furnace belongs to a high-temperature cracking tube furnace in an anaerobic environment, adopts the principle of indirect heat supply, and utilizes a heating mode of radiation heat transfer and convection heat transfer; under the condition of isolating air, organic materials input into the high-temperature cracking furnace are subjected to carbon chain fracture or dehydrogenation under the high-temperature action; the main structure of the high-temperature cracking furnace comprises: the device comprises a radiation chamber, a convection chamber, a waste heat recovery cooling system, a burner and a ventilation system;
The heating furnace belongs to a device for heating the high-temperature cracking furnace in the petrochemical industry, and can adopt gas heating, fuel oil heating and high-temperature plasma flame heating;
the waste heat steam boiler belongs to a tubular steam generator;
the desulfurization equipment belongs to gas desulfurization equipment in petrochemical industry;
the device for producing hydrogen by conversion belongs to the device for producing hydrogen and carbon dioxide under the action of a catalyst (namely a conversion catalyst) in a fixed bed by carbon monoxide and water vapor, such as the device for producing hydrogen by conversion of carbon monoxide in the ammonia synthesis industry;
the gas-liquid separation equipment belongs to gas-phase and liquid-phase separation equipment used in petrochemical industry, the gas is discharged from the upper part of the equipment, and the liquid phase (such as oil and water) is discharged from a side wall pipe orifice valve at the lower part of the equipment;
the liquid collecting device belongs to an oil-water collecting and buffering tank in petrochemical industry;
the gas purifying equipment belongs to the petrochemical industry and has the functions of desulfurization, dechlorination, tar removal and dust removal;
the hydrogen separation and purification equipment is one of the following equipment: (1) the method comprises the steps of (1) adopting an independent membrane separation hydrogen extraction device, (2) adopting an independent PSA pressure swing adsorption gas separation hydrogen purification device, (3) adopting a device for extracting hydrogen by the PSA device and then further recovering hydrogen extracted by the membrane separation device from tail gas after hydrogen extraction by the PSA device; (4) preferably, the invention adopts the equipment for separating and purifying hydrogen by adopting the liquid organic matter carrier, and the equipment mainly comprises a closed tank body I, a cooling equipment I, a heating equipment I and a gas dispersing equipment I; the top of the closed tank body I is provided with a gas outlet, the closed tank body I is internally provided with a liquid organic matter carrier, the cooling equipment I and the heating equipment I are arranged in the liquid organic matter carrier in the closed tank body I, the gas dispersing equipment I is arranged in the liquid organic matter carrier in the closed tank body I, and the gas dispersing equipment I is connected and communicated with the outlet of the compressor I through a hydrogen-rich combustible gas pipeline;
The fuel gas storage tank belongs to a fuel gas storage tank for petrochemical industry;
the hydrogen storage equipment is one of the following equipment: (1) the high-pressure gas storage device adopts a compressor to convey 99.99 percent (wt%) hydrogen released in the 6 hydrogen separation and purification device into a steel bottle for storage and standby, (2) a liquefied hydrogen storage device, (3) a metal hydride storage device, (4) a physical adsorption hydrogen storage device, (5) preferably, the invention utilizes a liquid organic matter carrier hydrogen storage device, namely a compressor II to convey 99.99 percent (wt%) hydrogen released in the hydrogen separation and purification device into the liquid organic matter carrier hydrogen storage device adopted by the invention through a hydrogen pipeline for hydrogen absorption and storage; the device for storing hydrogen by the liquid organic matter carrier mainly comprises a closed tank body II, a cooling device II, a heating device II and a gas dispersing device II; the top of the second closed tank body is provided with a hydrogen outlet, and the second closed tank body is internally provided with a liquid organic carrier; the second cooling device and the second heating device are arranged in a liquid organic matter carrier in the second closed tank body, the second gas dispersing device is arranged in the liquid organic matter carrier in the second closed tank body, and the second gas dispersing device is connected and communicated with the second outlet of the compressor through a hydrogen pipeline;
The shell-and-tube condenser; belongs to a shell-and-tube heat exchanger adopted by the petrochemical industry.
2. A method for preparing hydrogen from household garbage and/or organic matters comprises the following steps:
(1) Pretreatment: manually sorting household garbage and/or organic matters, breaking bags, removing iron by a magnetic separator, sieving or sorting to remove stone sediment, extruding, dehydrating or drying to obtain pretreated combustible matters;
(2) Pyrolysis gasification: loading the combustible material in the step (1) into a pyrolysis gasification furnace through a feeder for pyrolysis gasification; one of the following two methods is pyrolysis gasification under the condition of isolating oxygen, wherein the catalyst is adopted for pyrolysis gasification or catalyst-free pyrolysis gasification, gas phase products and carbon residue are obtained after the pyrolysis gasification, combustible gas generated by the pyrolysis gasification is led out of a pyrolysis gasification furnace, and the carbon residue is discharged; the other is to use air (or oxygen) as gasifying agent, to make pyrolysis vaporization by using vertical pyrolysis vaporization furnace, to obtain gas phase product and slag after pyrolysis gasification, to lead the gas phase product generated by pyrolysis gasification out of the pyrolysis vaporization furnace, and to discharge slag from the pyrolysis vaporization furnace;
(3) High-temperature cracking: introducing the gas phase product generated by pyrolysis and gasification in the step (2) into a high-temperature cracking furnace for anaerobic high-temperature cracking at 1000-1300 ℃, or conveying organic liquid and organic gas into the high-temperature cracking furnace for anaerobic high-temperature cracking at 1000-1300 ℃; the method comprises the steps of heating a high-temperature cracking furnace by adopting an indirect heat supply principle in a radiation heat transfer and convection heat transfer mode, introducing a proper amount of water vapor, directly triggering raw water gas reaction by the water vapor and a gas phase product, cracking and dehydrogenating a gas phase product generated by pyrolysis and gasification through high-temperature cracking, removing carbon residues generated by high-temperature cracking through the water gas reaction of the water vapor to obtain high-temperature combustible gas, and leading the combustible gas out of the high-temperature cracking furnace;
(4) Cooling and desulfurizing: cooling the high-temperature combustible gas discharged from the step (3) by adopting water in a waste heat steam boiler to absorb heat to generate steam, or cooling the high-temperature combustible gas by adopting a mode of preheating a gas-phase product of the step (2), and then carrying out desulfurization treatment on the combustible gas;
(5) And (3) hydrogen production by conversion: delivering the desulfurized combustible gas in the step (4) into shift hydrogen production equipment, introducing a proper amount of steam, carrying out shift reaction on carbon monoxide in the combustible gas and the steam under the action of a shift catalyst to produce hydrogen and carbon dioxide, obtaining hydrogen-rich combustible gas, and leading the hydrogen-rich combustible gas produced after the shift reaction out of the shift hydrogen production equipment;
(6) Condensing, separating and purifying hydrogen-rich fuel gas: the hydrogen-rich combustible gas led out of the hydrogen production equipment (5) is conveyed to gas-liquid separation equipment for gas-liquid separation after heat exchange to room temperature by a condenser, the hydrogen-rich combustible gas discharged from the gas-liquid separation equipment is led into gas purification equipment for purification treatment to remove carbon dioxide in the hydrogen-rich combustible gas, the purified hydrogen-rich combustible gas is led out of the gas purification equipment, liquid in the gas-liquid separation equipment is discharged from a liquid outlet at the lower part of the gas-liquid separation equipment, and the discharged liquid is collected and treated;
(7) And (3) hydrogen purification: introducing the purified hydrogen-rich combustible gas in the step (6) into hydrogen separation and purification equipment, and selecting one of the following methods to separate and purify hydrogen: (1) purifying hydrogen by membrane separation, (2) purifying hydrogen by PSA pressure swing adsorption gas separation, (3) extracting hydrogen by PSA, and then performing membrane separation on tail gas after PSA process to extract residual hydrogen in tail gas after PAS; after membrane separation or PSA separation, 99.99% (wt%) pure hydrogen and other combustible gases are obtained, and the pure hydrogen and other combustible gases are respectively discharged from the hydrogen separation and purification equipment; (4) preferably, the technology of selectively absorbing and storing hydrogen as a liquid organic matter carrier is adopted to separate and purify hydrogen, and the selectively absorbing and storing hydrogen as a liquid organic matter carrier belongs to a composite liquid organic matter carrier; inputting the purified hydrogen-rich combustible gas in the step (6) into a closed tank body I filled with a liquid organic matter carrier through a compressor I and a hydrogen-rich gas pipeline, absorbing hydrogen in the hydrogen-rich combustible gas by the liquid organic matter carrier, continuously storing the hydrogen in the closed tank body I, and continuously discharging the hydrogen-rich combustible gas from the closed tank body I and conveying the hydrogen-rich combustible gas into a gas storage tank for storage, wherein other combustible gases cannot be absorbed and stored by the liquid organic matter carrier; a first cooling device is arranged in the first closed tank body, and the cooling medium flowing in the first cooling device is used for cooling the heat released in the process of absorbing the hydrogen; the hydrogen release belongs to endothermic reaction, heating is carried out in the process of releasing the hydrogen by utilizing a heating medium flowing in a heating device I arranged in a closed tank I, 99.99 percent (wt%) of the hydrogen is released from a liquid organic matter carrier, and the hydrogen is released and discharged from the closed tank I;
(8) Hydrogen storage: hydrogen storage was carried out by one of two methods: (1) a compressor is adopted to convey the hydrogen released in the hydrogen separation and purification equipment (7) into a steel bottle for storage for standby; (2) storing hydrogen by adopting a liquid organic matter carrier; a second compressor is used for conveying 99.99 percent (wt%) hydrogen released in the hydrogen separation and purification equipment (7) into a second closed tank body filled with a liquid organic carrier for absorption and storage, the absorption and storage of hydrogen belongs to exothermic reaction, and the cooling is favorable for the absorption and storage of hydrogen; the heat released in the process of absorbing the hydrogen is cooled by using a cooling medium flowing in cooling equipment II in the closed tank body II; and (3) releasing hydrogen, heating the liquid organic matter carrier by using a heating device II arranged in the sealed tank II, overflowing the hydrogen adsorbed and stored in the liquid organic matter carrier, releasing the hydrogen from a hydrogen outlet of the sealed tank II, and collecting and utilizing the released hydrogen.
3. The method for preparing hydrogen from household garbage and/or organic matters according to claim 2, wherein the method comprises the following steps: the liquid organic matter carrier belongs to a composite liquid organic matter carrier, and is characterized in that: is prepared from petroleum ether (90-120 deg.C) 30 wt% and amyl alcohol 70 wt%, and through mixing.
4. The method for preparing hydrogen from household garbage and/or organic matters according to claim 2, wherein the method comprises the following steps: the household garbage and/or organic matters comprise: household garbage, kitchen garbage, agriculture and forestry and animal husbandry organic waste, industrial organic waste, straw, methanol, methane, fuel oil, coal tar, sludge, oil extraction plant oil sludge, oil sand, chinese honeylocust, animal and vegetable oil and landfill organic waste.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN117264661A (en) * | 2023-10-16 | 2023-12-22 | 南京工业大学 | Device and method for producing hydrogen by biomass fuel based on inorganic membrane |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN117264661A (en) * | 2023-10-16 | 2023-12-22 | 南京工业大学 | Device and method for producing hydrogen by biomass fuel based on inorganic membrane |
| CN117264661B (en) * | 2023-10-16 | 2024-04-26 | 南京工业大学 | Device and method for producing hydrogen by biomass fuel based on inorganic membrane |
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