CN114437833A - Biomass hydrogen production method and system - Google Patents
Biomass hydrogen production method and system Download PDFInfo
- Publication number
- CN114437833A CN114437833A CN202011193768.7A CN202011193768A CN114437833A CN 114437833 A CN114437833 A CN 114437833A CN 202011193768 A CN202011193768 A CN 202011193768A CN 114437833 A CN114437833 A CN 114437833A
- Authority
- CN
- China
- Prior art keywords
- biomass
- hydrogen
- reactor
- reaction
- hydrogen production
- 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.)
- Granted
Links
- 239000001257 hydrogen Substances 0.000 title claims abstract description 139
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 139
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 138
- 239000002028 Biomass Substances 0.000 title claims abstract description 119
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 69
- 238000006243 chemical reaction Methods 0.000 claims abstract description 102
- 239000007789 gas Substances 0.000 claims abstract description 87
- 238000002309 gasification Methods 0.000 claims abstract description 80
- 239000000571 coke Substances 0.000 claims abstract description 62
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 62
- 238000003763 carbonization Methods 0.000 claims abstract description 35
- 239000003054 catalyst Substances 0.000 claims abstract description 28
- 238000001179 sorption measurement Methods 0.000 claims abstract description 26
- 239000000203 mixture Substances 0.000 claims abstract description 19
- 238000002156 mixing Methods 0.000 claims abstract description 17
- 239000002994 raw material Substances 0.000 claims abstract description 16
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 claims description 18
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 16
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 14
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 12
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 claims description 12
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 claims description 12
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 10
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 10
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 claims description 10
- -1 alkaline earth metal carbonate Chemical class 0.000 claims description 8
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 8
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 8
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 8
- 239000001103 potassium chloride Substances 0.000 claims description 8
- 235000011164 potassium chloride Nutrition 0.000 claims description 8
- 229910001508 alkali metal halide Inorganic materials 0.000 claims description 7
- 150000008045 alkali metal halides Chemical class 0.000 claims description 7
- 239000011780 sodium chloride Substances 0.000 claims description 7
- 239000001095 magnesium carbonate Substances 0.000 claims description 6
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 6
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 6
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 claims description 4
- KQHXBDOEECKORE-UHFFFAOYSA-L beryllium sulfate Chemical compound [Be+2].[O-]S([O-])(=O)=O KQHXBDOEECKORE-UHFFFAOYSA-L 0.000 claims description 4
- XJHCXCQVJFPJIK-UHFFFAOYSA-M caesium fluoride Chemical compound [F-].[Cs+] XJHCXCQVJFPJIK-UHFFFAOYSA-M 0.000 claims description 4
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 claims description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 4
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 4
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Chemical compound [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 claims description 4
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 4
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 4
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 4
- JAAGVIUFBAHDMA-UHFFFAOYSA-M rubidium bromide Chemical compound [Br-].[Rb+] JAAGVIUFBAHDMA-UHFFFAOYSA-M 0.000 claims description 4
- FGDZQCVHDSGLHJ-UHFFFAOYSA-M rubidium chloride Chemical compound [Cl-].[Rb+] FGDZQCVHDSGLHJ-UHFFFAOYSA-M 0.000 claims description 4
- AHLATJUETSFVIM-UHFFFAOYSA-M rubidium fluoride Chemical compound [F-].[Rb+] AHLATJUETSFVIM-UHFFFAOYSA-M 0.000 claims description 4
- WFUBYPSJBBQSOU-UHFFFAOYSA-M rubidium iodide Chemical compound [Rb+].[I-] WFUBYPSJBBQSOU-UHFFFAOYSA-M 0.000 claims description 4
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 4
- 235000009518 sodium iodide Nutrition 0.000 claims description 4
- UBXAKNTVXQMEAG-UHFFFAOYSA-L strontium sulfate Chemical compound [Sr+2].[O-]S([O-])(=O)=O UBXAKNTVXQMEAG-UHFFFAOYSA-L 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- HOTRSNBZKAJMEW-UHFFFAOYSA-M [Br-].[Fr+] Chemical compound [Br-].[Fr+] HOTRSNBZKAJMEW-UHFFFAOYSA-M 0.000 claims description 2
- ROZPZBUZWPOKFI-UHFFFAOYSA-M [Cl-].[Fr+] Chemical compound [Cl-].[Fr+] ROZPZBUZWPOKFI-UHFFFAOYSA-M 0.000 claims description 2
- REHSTLKSMMQUJZ-UHFFFAOYSA-M [F-].[Fr+] Chemical compound [F-].[Fr+] REHSTLKSMMQUJZ-UHFFFAOYSA-M 0.000 claims description 2
- BGVAXUQNVLJVFE-UHFFFAOYSA-M [I-].[Fr+] Chemical compound [I-].[Fr+] BGVAXUQNVLJVFE-UHFFFAOYSA-M 0.000 claims description 2
- YPWICUOZSQYGTD-UHFFFAOYSA-L [Ra+2].[O-]C([O-])=O Chemical compound [Ra+2].[O-]C([O-])=O YPWICUOZSQYGTD-UHFFFAOYSA-L 0.000 claims description 2
- MXQFUMUIEZBICJ-UHFFFAOYSA-L [Ra+2].[O-]S([O-])(=O)=O Chemical compound [Ra+2].[O-]S([O-])(=O)=O MXQFUMUIEZBICJ-UHFFFAOYSA-L 0.000 claims description 2
- 150000001342 alkaline earth metals Chemical group 0.000 claims description 2
- ZBUQRSWEONVBES-UHFFFAOYSA-L beryllium carbonate Chemical compound [Be+2].[O-]C([O-])=O ZBUQRSWEONVBES-UHFFFAOYSA-L 0.000 claims description 2
- 229910000023 beryllium carbonate Inorganic materials 0.000 claims description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 229910052792 caesium Inorganic materials 0.000 claims description 2
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 2
- LYQFWZFBNBDLEO-UHFFFAOYSA-M caesium bromide Chemical compound [Br-].[Cs+] LYQFWZFBNBDLEO-UHFFFAOYSA-M 0.000 claims description 2
- AIYUHDOJVYHVIT-UHFFFAOYSA-M caesium chloride Chemical compound [Cl-].[Cs+] AIYUHDOJVYHVIT-UHFFFAOYSA-M 0.000 claims description 2
- XQPRBTXUXXVTKB-UHFFFAOYSA-M caesium iodide Chemical compound [I-].[Cs+] XQPRBTXUXXVTKB-UHFFFAOYSA-M 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- 229910052730 francium Inorganic materials 0.000 claims description 2
- KLMCZVJOEAUDNE-UHFFFAOYSA-N francium atom Chemical compound [Fr] KLMCZVJOEAUDNE-UHFFFAOYSA-N 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 claims description 2
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 239000011698 potassium fluoride Substances 0.000 claims description 2
- 235000003270 potassium fluoride Nutrition 0.000 claims description 2
- 229910052701 rubidium Inorganic materials 0.000 claims description 2
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 claims description 2
- 229940102127 rubidium chloride Drugs 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011775 sodium fluoride Substances 0.000 claims description 2
- 235000013024 sodium fluoride Nutrition 0.000 claims description 2
- 229910000018 strontium carbonate Inorganic materials 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims 2
- 150000004820 halides Chemical class 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 38
- 230000008569 process Effects 0.000 abstract description 28
- 230000004907 flux Effects 0.000 description 14
- 238000005303 weighing Methods 0.000 description 14
- 239000010902 straw Substances 0.000 description 12
- 238000002485 combustion reaction Methods 0.000 description 8
- 241000124033 Salix Species 0.000 description 6
- 240000008042 Zea mays Species 0.000 description 6
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 6
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 6
- 235000005822 corn Nutrition 0.000 description 6
- 241000209140 Triticum Species 0.000 description 5
- 235000021307 Triticum Nutrition 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 4
- 235000017491 Bambusa tulda Nutrition 0.000 description 4
- 241001330002 Bambuseae Species 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical group [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 4
- 241000218657 Picea Species 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 239000011425 bamboo Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 239000003463 adsorbent Substances 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 150000001340 alkali metals Chemical group 0.000 description 3
- 238000004523 catalytic cracking Methods 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000002803 fossil fuel Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 240000009226 Corylus americana Species 0.000 description 2
- 235000001543 Corylus americana Nutrition 0.000 description 2
- 235000007466 Corylus avellana Nutrition 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 240000007049 Juglans regia Species 0.000 description 2
- 235000009496 Juglans regia Nutrition 0.000 description 2
- 241000218652 Larix Species 0.000 description 2
- 235000005590 Larix decidua Nutrition 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000001833 catalytic reforming Methods 0.000 description 2
- 239000003610 charcoal Substances 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000002737 fuel gas Substances 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- 230000002427 irreversible effect Effects 0.000 description 2
- 229910001507 metal halide Inorganic materials 0.000 description 2
- 150000005309 metal halides Chemical class 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000002006 petroleum coke Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 235000020234 walnut Nutrition 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 229910003264 NiFe2O4 Inorganic materials 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
- C10J3/58—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels combined with pre-distillation of the fuel
- C10J3/60—Processes
- C10J3/64—Processes with decomposition of the distillation products
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
- C01B3/12—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of water vapour with carbon monoxide
- C01B3/16—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of water vapour with carbon monoxide using catalysts
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
- 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
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/042—Purification by adsorption on solids
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/0465—Composition of the impurity
- C01B2203/0475—Composition of the impurity the impurity being carbon dioxide
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1076—Copper or zinc-based catalysts
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J2300/00—Details of gasification processes
- C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
- C10J2300/0913—Carbonaceous raw material
- C10J2300/0916—Biomass
- C10J2300/092—Wood, cellulose
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J2300/00—Details of gasification processes
- C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
- C10J2300/0953—Gasifying agents
- C10J2300/0973—Water
- C10J2300/0976—Water as steam
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J2300/00—Details of gasification processes
- C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
- C10J2300/0983—Additives
- C10J2300/0986—Catalysts
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J2300/00—Details of gasification processes
- C10J2300/16—Integration of gasification processes with another plant or parts within the plant
- C10J2300/164—Integration of gasification processes with another plant or parts within the plant with conversion of synthesis gas
- C10J2300/1656—Conversion of synthesis gas to chemicals
Abstract
The invention discloses a biomass hydrogen production method and a biomass hydrogen production system, wherein the hydrogen production method comprises the following steps: (1) the biomass raw material enters a carbonization reactor for reaction to obtain biological coke and volatile gas; (2) and (2) uniformly mixing the biological coke obtained in the step (1) with a gasification catalyst, then feeding the mixture into a gasification reactor, contacting with steam for reaction, and further carrying out steam shift reaction and pressure swing adsorption treatment on the gasified gas obtained by the reaction to obtain a hydrogen product. The biomass hydrogen production system comprises a carbonization reactor, a gasification reactor, a water-vapor shift reactor and a pressure swing adsorption device. The biomass hydrogen production method and the biomass hydrogen production system convert the biomass into the hydrogen product through the carbonization-gasification combined process, and have the advantages of simple process, high hydrogen yield and high energy utilization rate.
Description
Technical Field
The invention relates to the technical field of biomass utilization, in particular to a method for preparing hydrogen by a biomass carbonization-gasification combined process.
Background
Hydrogen is an ideal clean energy source, is nontoxic and odorless, generates pure water when being combusted with oxygen, and has zero pollution to the environment. The main method for preparing hydrogen at present is to prepare hydrogen by using fossil fuel, but the resource of the fossil fuel is limited, and the pollution to the environment is almost irreversible, so that a new hydrogen preparation raw material and a hydrogen preparation process must be developed. Biomass hydrogen production with renewability and abundant reserves is favored. The advantages of biomass hydrogen production are mainly embodied in the following two aspects: the biomass is a crystallization energy source for realizing zero emission of carbon dioxide, can effectively reduce the emission of greenhouse gases and harmful gases, and links the irreversible pollution to the world environment caused by the use of fossil fuels. On the other hand, the biomass reserves are abundant and can be regenerated, and the total amount of biomass growing on the earth every year is 1400-1800 hundred million tons, which is equivalent to 10 times of the total energy consumption in the world at present. The development of the biomass hydrogen production technology can effectively develop and utilize the resource treasury and has strategic significance of sustainable development.
At present, the research of biomass hydrogen production mainly focuses on two aspects of thermochemical conversion hydrogen production and biological hydrogen production, the biological hydrogen production has the problems of low light energy conversion efficiency, feedback inhibition of volatile acid, product inhibition among hydrogen production bacteria and the like, so that the hydrogen production efficiency is low, and the thermochemical conversion hydrogen production is more suitable for large-scale hydrogen production.
The invention with the publication number of CN1435368A discloses a method for preparing hydrogen by catalytic cracking of biomass, which takes air or/and water vapor as working gas and animal and plant raw materials with certain particle size as biomass raw materials, a fluidized bed reactor comprises a combustion zone, a catalytic gasification zone and a friend-making catalytic cracking zone, wherein a catalytic cracking catalyst is an iron catalyst, a water gas shift catalyst is an alkali metal catalyst, a tar cracking catalyst is a nickel-based catalyst, the catalysts are suspended in different zones of the reactor under the action of air flow, so as to generate hydrogen-rich fuel gas containing more than 70% of hydrogen, and the hydrogen-rich fuel gas is purified by a fixed bed tar cracker after dust is removed by a cyclone separator. However, the process has the defects of high gasification temperature, high energy consumption, high equipment requirement, high price of the alkali metal catalyst and the nickel-based catalyst, harsh use conditions and the like.
The patent CN 105692551B continuously sends biomass and steam into a fluidized bed reactor for rapid cracking at 600 ℃, the generated cracked gas, biomass charcoal and steam enter a fluidized bed reactor together for synchronous gasification reaction of the cracked gas and the biomass charcoal, the gas from the fluidized bed reactor is subjected to catalytic reforming reaction to generate hydrogen-rich gas, the catalytic reforming adopts Co and Cu based modified catalysts, and the defects of harsh gasification reaction conditions of the biomass steam and high price of the reforming catalysts exist.
Patent CN 104194834B provides a biomass chemical-looping hydrogen production device, which uses NiFe2O4The oxygen carrier is used for chemical-looping hydrogen production, and has the problems of high price, long cycle service life, reaction activity and the like. Therefore, the development of new thermochemical conversion hydrogen production processes, inexpensive catalysts, and reduction of energy consumption in hydrogen production processes remain important and difficult points of research.
Disclosure of Invention
In order to solve the technical problems, the invention provides a method and a system for preparing hydrogen from biomass, which convert the biomass into a hydrogen product by a carbonization-gasification combined process and have the advantages of simple process, high hydrogen yield and high energy utilization rate.
The specific technical scheme is as follows:
a method for producing hydrogen from biomass, which comprises the following steps:
(1) the biomass raw material enters a carbonization reactor for reaction to obtain biological coke and volatile gas;
(2) and (2) uniformly mixing the biological coke obtained in the step (1) with a gasification catalyst, then feeding the mixture into a gasification reactor, contacting with steam for reaction, and further carrying out steam shift reaction and pressure swing adsorption treatment on the gasified gas obtained by the reaction to obtain a hydrogen product.
In the above method for producing hydrogen from biomass, the biomass raw material may be derived from any substance containing lignocellulose, such as forestry residues or agricultural residues, and further specifically may be any substance containing lignocellulose, such as straw, rice hull, wheat straw, wood block, leaves, branches, and the like. The shape of the raw material can be any shape including sheet, round, cylinder, cone, square, irregular shape and the like, and the maximum dimension of the raw material in the direction is not more than 30mm, preferably 1-25 mm.
In the method for preparing hydrogen from biomass, volatile gas from the carbonization reactor enters the combustor to be fully combusted, and heat generated by combustion is supplied to the carbonization reactor, the gasification reactor and the water vapor generator for use.
In the method for preparing hydrogen from biomass, the biomass raw material in the step (1) is subjected to pyrolysis and carbonization reactions in a carbonization reactor, wherein the reaction temperature is 200-550 ℃, and preferably 250-450 ℃.
In the method for producing hydrogen from biomass, the gasification catalyst in the step (2) comprises a component A and a component B, wherein the component A is an alkali metal halide, the component B is an alkaline earth metal sulfate or an alkaline earth metal carbonate, and the mass ratio of the component A to the component B is 30: 1-1: 5, preferably 6: 1-1: 1.
in the above method for producing hydrogen from biomass, the alkali metal element in the alkali metal halide may be one or more of lithium, sodium, potassium, rubidium, cesium, and francium; the halogen in the alkali metal halide may be one or more of fluorine, chlorine, bromine and iodine, and further, the specific alkali metal halide may be selected from one or more of lithium chloride, sodium chloride, potassium chloride, rubidium chloride, cesium chloride, francium chloride, lithium fluoride, sodium fluoride, potassium fluoride, rubidium fluoride, cesium fluoride, francium fluoride, lithium bromide, sodium bromide, potassium bromide, rubidium bromide, cesium bromide, francium bromide, lithium iodide, sodium iodide, potassium iodide, rubidium iodide, cesium iodide and francium iodide, and preferably is one or more of sodium chloride, potassium chloride, sodium bromide, potassium bromide, sodium iodide and potassium iodide.
In the method for producing hydrogen by using biomass, the alkaline earth metal sulfate is one or more of beryllium sulfate, magnesium sulfate, calcium sulfate, strontium sulfate, barium sulfate and radium sulfate, and preferably one or more of magnesium sulfate, calcium sulfate and barium sulfate.
In the method for producing hydrogen by using biomass, the alkaline earth metal carbonate is one or more of beryllium carbonate, magnesium carbonate, calcium carbonate, strontium carbonate, barium carbonate and radium carbonate, and preferably one or more of magnesium carbonate and calcium carbonate.
In the method for producing hydrogen by biomass, the gasification reaction conditions in the step (2) are as follows: the reaction temperature is 700-950 ℃, preferably 750-900 ℃, and the flow rate of the water is 0.05-0.8 mL/min.
In the method for producing hydrogen by using biomass, the mass ratio of the biological coke gasification catalyst to the biomass raw material in the step (2) is 60-1: 99 to 40.
In the above method for producing hydrogen from biomass, the water-gas shift reaction in step (2) adopts the existing water-gas shift process in the art, and the catalyst used in the water-gas shift reaction may be a commercially available product, or may be prepared according to the methods disclosed in the patents or documents in the existing art, for example, a copper-based low-temperature shift catalyst B208 and the like may be specifically used. In general, the reaction conditions of the steam shift device are as follows: the reaction temperature is 250-300 ℃, the volume ratio of the water vapor to the gasified gas is 0.5-0.9, and the space velocity of the gasified gas is 1500-2500 h-1。
In the above method for producing hydrogen from biomass, the pressure swing adsorption in step (2) adopts the existing pressure swing adsorption device in the field, and the pressure swing adsorption device is filled with an adsorbent, which may be one or more of petroleum coke-based activated carbon, molecular sieve, silica gel and activated alumina. The operating conditions of the pressure swing adsorption unit are typically: the pressure is 1.5-4 MPa, and the temperature is 20-30 ℃.
In a second aspect, the invention provides a biomass hydrogen production system comprising
The carbonization reactor is used for receiving the biomass raw material and obtaining biological coke and volatile gas after treatment;
the gasification reactor is used for receiving the biological coke, the gasification catalyst and the water vapor from the carbonization reactor, and obtaining gasified gas after treatment;
the water-vapor shift reactor is used for receiving the gasified gas from the gasification reactor and obtaining hydrogen-containing body after treatment;
the pressure swing adsorption device is used for receiving the hydrogen-containing gas from the water-vapor shift reactor and obtaining a hydrogen product after treatment.
In the biomass hydrogen production system, the system comprises the combustor, the combustor is used for receiving and combusting volatile gas from the carbonization reactor, and huge heat generated by combustion of the volatile gas is supplied to the carbonization reactor, the gasification reactor and the steam generator, so that heat and reaction temperature are provided for hydrogen production reaction, energy supply of the whole process is assisted, and stable operation of the reaction is guaranteed.
Compared with the prior art, the biomass hydrogen production method and the biomass hydrogen production system have the following beneficial technical effects:
1. in the biomass hydrogen production method, the alkaline metal halide and the alkaline earth metal sulfate or the alkaline earth metal carbonate are used as gasification catalysts in the biological coke gasification process, and the metastable active component group is generated in the biological coke steam gasification system through reactions such as in-situ ion exchange, hydrolysis, reduction and the like, so that the hydrogen production reaction activity of the biological coke is greatly improved, and the problem of low catalytic activity of a cheap alkaline metal halide catalytic material is solved. The adopted catalytic material has wide sources, can be obtained from natural ores and seawater, has low price, greatly reduces the catalytic cost of the biological coke steam gasification, can be recycled and reused by a water-soluble method, and can also be used as a disposable catalyst.
2. In the method for preparing hydrogen from biomass, the biomass raw material is converted into the hydrogen product by the carbonization-gasification combined treatment process, and the method has the advantages of simple process, high hydrogen yield and high energy utilization rate.
3. In the biomass hydrogen production method, the biomass carbonization reaction temperature is controlled below 550 ℃, and the polycondensation reaction of heavy tar can be ensured as much as possible by adjusting the temperature and the residence time of the biomass in the carbonization furnace, so that the yield of the biological coke is maximized.
4. In the invention, the volatile components generated in the biomass carbonization reactor are fed into the combustion furnace for combustion in a high-temperature state, and the tar components are combusted with combustible gas in a gas state, so that the environmental pollution caused by tar discharge and gas purification is avoided, the problem of pipeline blockage caused by tar condensation is prevented, the problem of oil-gas separation is solved, and the reaction steps are greatly simplified. The heat accumulating type heat exchanger supplies huge heat generated by burning of the volatile components to the water vapor generator, the biomass carbonization reactor and the biological coke gasification reactor, provides heat and reaction temperature for hydrogen production reaction, assists energy supply of the whole process, and ensures stable operation of reaction.
Detailed Description
In the embodiment and the comparative example of the invention, the water-gas shift reaction adopts a copper-based low-temperature shift catalyst B208 with the composition of CuO/ZnO/Al2O3(mass fraction of CuO 38%, mass fraction of ZnO 40%, Al2O38 percent of mass fraction), 20-40 meshes of catalyst granularity and 10mL of catalyst loading. The biological coke gasification gas enters a water vapor conversion device and then reacts with the water vapor simultaneously entering a reaction tank at 260 ℃, the flow ratio of the water vapor to the gasification gas is 0.7, and the space velocity of the gasification gas is 2000h-1。
In the embodiment of the present invention and the comparative example, the pressure swing adsorption process is: the operating conditions of the water-vapor conversion device are 2Mpa of pressure and 25 ℃, and the adsorbent is a graded adsorbent consisting of petroleum coke-based active carbon, a molecular sieve, silica gel and active alumina according to the mass ratio of 5:2:1: 1.
In the embodiment of the invention, the volatile components generated in the biomass carbonization reactor are fed into the combustion furnace in a high-temperature state for combustion, and the huge heat generated by the combustion of the volatile components is supplied to the water vapor generator, the biomass carbonization reactor and the biological coke gasification reactor through the heat accumulating type heat exchanger, so that the energy supply of the whole process is ensured, the energy consumption of the process is greatly reduced, and the stable operation of the reaction can be ensured only by a small amount of auxiliary heating.
Example 1
Weighing 37g of wheat straw, adding the wheat straw into a biomass carbonization reactor for reaction at the temperature of 350 ℃, and reacting the generated biological coke with 3g of KCl and 0.1g of MgCO3Uniformly mixing in a spiral feeder, and entering a biological coke gasification reactor for steam gasification reaction under the following reaction conditions: the temperature is 750 ℃, the pressure is normal, the flux of water is 0.3mL/min, and the gas composition at the outlet of the biological coke gasification reactor is H2The volume fraction is 55.1 percent, the concentration of hydrogen in the gasified gas is further improved by the water-vapor shift reactor, and H is contained in the gas at the outlet of the water-vapor shift reactor2The volume fraction reaches 64.2 percent, the hydrogen concentration can be increased to 99 percent through pressure swing adsorption, and the biomass hydrogen production rate of the whole process is 63g/kg biomass.
Example 2
Weighing 35g of corn straws, adding the corn straws into a biomass carbonization reactor for reaction at the temperature of 450 ℃, wherein the biological coke generated by the reaction is mixed with 1.5g of NaCl and 0.6g of CaCO3Uniformly mixing in a spiral feeder, and entering a biological coke gasification reactor for steam gasification reaction under the following reaction conditions: the temperature is 800 ℃, the pressure is normal, the flux of water is 0.6mL/min, and the gas composition at the outlet of the biological coke gasification reactor is H2The volume fraction of the gasified gas is 54.1 percent, the concentration of hydrogen in the gas is further improved by the gasified gas passing through a water-vapor shift reactor, and H is contained in the gas at the outlet of the water-vapor shift reactor2The volume fraction reaches 62.3 percent, the hydrogen concentration can be increased to 99 percent through pressure swing adsorption, and the biomass hydrogen production rate of the whole process is 96g hydrogen/kg biomass.
Example 3
Weighing 39g of bamboo willow, adding the bamboo willow into a biomass carbonization reactor for reaction at the temperature of 550 ℃, and reacting the generated biological coke with 1.6g of NaBr and 0.2g of MgCO3、0.8gCaCO3Uniformly mixing in a spiral feeder, and entering a biological coke gasification reactor for steam gasification reaction under the following reaction conditions: the temperature is 850 ℃, the pressure is normal, the flux of water is 0.45mL/min, and the gas composition at the outlet of the biological coke gasification reactor is H2The volume fraction is 51.1 percent, the concentration of hydrogen in the gasified gas is further improved through a water-vapor shift reactor, and the gasified gas is subjected to water-vapor shift reactionH in gas at the outlet of the device2The volume fraction reaches 62.5 percent, the hydrogen concentration can be increased to 99 percent through pressure swing adsorption, and the biomass hydrogen production rate of the whole process is 85g of hydrogen/kg of biomass.
Example 4
Weighing 40g of hazelnut, adding the hazelnut into a biomass carbonization reactor for reaction at the reaction temperature of 300 ℃, wherein the biological coke generated by the reaction is 0.4g of KCl and 1.5g of CaCO3Uniformly mixing in a spiral feeder, and entering a biological coke gasification reactor for steam gasification reaction under the following reaction conditions: the temperature is 950 ℃, the pressure is normal, the flux of water is 0.6mL/min, and the gas composition at the outlet of the biological coke gasification reactor is H2The volume fraction is 57.4 percent, the concentration of hydrogen in the gasified gas is further improved by the water-vapor shift reactor, and H is contained in the gas at the outlet of the water-vapor shift reactor2The volume fraction reaches 62.3 percent, the hydrogen concentration can be increased to 99 percent through pressure swing adsorption, and the biomass hydrogen production rate of the whole process is 42g of hydrogen/kg of biomass.
Example 5
Weighing 38g of walnut shells, adding the walnut shells into a biomass carbonization reactor for reaction at the temperature of 400 ℃, and reacting the generated biological coke with 1.4g of KBr and 1.1g of MgCO3Uniformly mixing in a spiral feeder, and entering a biological coke gasification reactor for steam gasification reaction under the following reaction conditions: the temperature is 900 ℃, the pressure is normal, the flux of water is 0.5mL/min, and the gas composition at the outlet of the biological coke gasification reactor is H2The volume fraction is 53.2 percent, the concentration of hydrogen in the gasified gas is further improved by the water-vapor shift reactor, and H is contained in the gas at the outlet of the water-vapor shift reactor2The volume fraction reaches 62.8 percent, the hydrogen concentration can be increased to 99 percent through pressure swing adsorption, and the biomass hydrogen production rate of the whole process is 90g hydrogen/kg biomass.
Example 6
Weighing 35g of wheat straw, adding the wheat straw into a biomass carbonization reactor for reaction at the temperature of 350 ℃, and reacting the generated biological coke with 2.8g of KCl and 0.1g of MgSO 24Uniformly mixing in a spiral feeder, and entering a biological coke gasification reactor for steam gasification reaction under the following reaction conditions: the temperature is 750 ℃, the pressure is normal, and the flux of water is 0.45mL/min, and the gas composition at the outlet of the biological coke gasification reactor is H2The volume fraction is 54.1 percent, the gasified gas passes through a water-vapor shift reactor to further improve the hydrogen concentration in the gas, and H is contained in the gas at the outlet of the water-vapor shift reactor2The volume fraction reaches 61.2 percent, the hydrogen concentration can be increased to 99 percent through pressure swing adsorption, and the biomass hydrogen production rate of the whole process is 58g/kg biomass.
Example 7
Weighing 42g of spruce scales, adding the spruce scales into a biomass carbonization reactor for reaction at the temperature of 450 ℃, and reacting the generated biological coke with 1.9g of NaCl and 1.1g of MgSO4Uniformly mixing in a spiral feeder, and entering a biological coke gasification reactor for steam gasification reaction under the following reaction conditions: the temperature is 800 ℃, the pressure is normal, the flux of water is 0.35mL/min, and the gas composition at the outlet of the biological coke gasification reactor is H2The volume fraction is 53.1 percent, the concentration of hydrogen in the gasified gas is further improved by the water-vapor shift reactor, and H is contained in the gas at the outlet of the water-vapor shift reactor2The volume fraction reaches 62.9 percent, the hydrogen concentration can be increased to 99 percent through pressure swing adsorption, and the biomass hydrogen production rate of the whole process is 93g hydrogen/kg biomass.
Example 8
Weighing 37g of larch, adding the larch into a biomass carbonization reactor for reaction at the temperature of 550 ℃, wherein the biological coke generated by the reaction is mixed with 2.1g of KBr and 0.3g of CaSO4、0.7gMgSO4Uniformly mixing in a spiral feeder, and entering a biological coke gasification reactor for steam gasification reaction under the following reaction conditions: the temperature is 850 ℃, the pressure is normal, the flux of water is 0.55mL/min, and the gas composition at the outlet of the biological coke gasification reactor is H2The volume fraction is 53.4 percent, the concentration of hydrogen in the gasified gas is further improved by the water-vapor shift reactor, and H is contained in the gas at the outlet of the water-vapor shift reactor2The volume fraction reaches 62.6 percent, the hydrogen concentration can be increased to 99 percent through pressure swing adsorption, and the biomass hydrogen production rate of the whole process is 82g of hydrogen/kg of biomass.
Example 9
Weighing 39g of willow, adding the willow into a biomass carbonization reactor for reaction at the reaction temperature of 300 ℃,the biological coke generated by the reaction is mixed with 0.4g of KCl and 1.5g of MgSO4Uniformly mixing in a spiral feeder, and entering a biological coke gasification reactor for steam gasification reaction under the following reaction conditions: the temperature is 950 ℃, the pressure is normal, the flux of water is 0.6mL/min, and the gas composition at the outlet of the biological coke gasification reactor is H2The volume fraction is 57.2 percent, the concentration of hydrogen in the gasified gas is further improved by the water-vapor shift reactor, and H is contained in the gas at the outlet of the water-vapor shift reactor2The volume fraction reaches 59.3 percent, the hydrogen concentration can be increased to 99 percent through pressure swing adsorption, and the biomass hydrogen production rate of the whole process is 46g hydrogen/kg biomass.
Example 10
Weighing 38g of corn straws, adding the corn straws into a biomass carbonization reactor for reaction at the reaction temperature of 400 ℃, and reacting the generated biological coke with 1.4g of KBr and 0.9g of MgSO (MgSO)4Uniformly mixing in a spiral feeder, and entering a biological coke gasification reactor for steam gasification reaction under the following reaction conditions: the temperature is 900 ℃, the pressure is normal, the water vapor flux is 0.5mL/min, and the gas composition at the outlet of the biological coke gasification reactor is H2The volume fraction is 53.0 percent, the concentration of hydrogen in the gasified gas is further improved by the water-vapor shift reactor, and H is contained in the gas at the outlet of the water-vapor shift reactor2The volume fraction reaches 62.7 percent, the hydrogen concentration can be increased to 99 percent through pressure swing adsorption, and the biomass hydrogen production rate of the whole process is 91g of hydrogen/kg of biomass.
Example 11
Weighing 125g of fir, adding the fir into a biomass carbonization reactor for reaction at the temperature of 300 ℃, wherein the biological coke generated by the reaction is mixed with 0.42g of KBr and 0.02g of CaCO3Uniformly mixing in a spiral feeder, and entering a biological coke gasification reactor for steam gasification reaction under the following reaction conditions: the temperature is 800 ℃, the pressure is normal, the flux of water is 0.5mL/min, and the gas composition at the outlet of the biological coke gasification reactor is H2The volume fraction is 48.9 percent, the concentration of hydrogen in the gasified gas is further improved by the water-vapor shift reactor, and H is contained in the gas at the outlet of the water-vapor shift reactor2The volume fraction reaches 60.3 percent, the hydrogen concentration can be improved to 97 percent through pressure swing adsorption, and the biomass production of the whole processThe hydrogen rate was 24g hydrogen/kg biomass.
Example 12
Weighing 41g of bamboo willow, adding the bamboo willow into a biomass carbonization reactor for reaction at the reaction temperature of 300 ℃, and reacting the generated biological coke with 10.2g of KBr and 50.8g of MgSO 44Uniformly mixing in a spiral feeder, and entering a biological coke gasification reactor for steam gasification reaction under the following reaction conditions: the temperature is 750 ℃, the pressure is normal, the flux of water is 0.3mL/min, and the gas composition at the outlet of the biological coke gasification reactor is H2The volume fraction is 57.5 percent, the concentration of hydrogen in the gasified gas is further improved by the water-vapor shift reactor, and H is contained in the gas at the outlet of the water-vapor shift reactor2The volume fraction reaches 64.8 percent, the hydrogen concentration can be increased to 99 percent through pressure swing adsorption, and the biomass hydrogen production rate of the whole process is 96g hydrogen/kg biomass.
Comparative example 1
Weighing 42g of spruce scales, adding the spruce scales into a biomass carbonization reactor for reaction at the temperature of 450 ℃, uniformly mixing biological coke generated by the reaction and 1.9g of NaCl in a spiral feeder, and allowing the mixture to enter a biological coke gasification reactor for steam gasification reaction under the following reaction conditions: the temperature is 800 ℃, the pressure is normal, the flux of water is 0.35mL/min, and the gas composition at the outlet of the biological coke gasification reactor is H2The volume fraction is 55.8 percent, the concentration of hydrogen in the gasified gas is further improved by the water-vapor shift reactor, and H is contained in the gas at the outlet of the water-vapor shift reactor2The volume fraction reaches 56.7 percent, the hydrogen concentration can be increased to 99 percent through pressure swing adsorption, and the biomass hydrogen production rate of the whole process is 64g hydrogen/kg biomass.
Comparative example 2
Weighing 35g of corn straws, adding the corn straws into a biomass carbonization reactor for reaction at the temperature of 450 ℃, wherein the biological coke generated by the reaction and 0.6g of CaCO3Uniformly mixing in a spiral feeder, and entering a biological coke gasification reactor for steam gasification reaction under the following reaction conditions: the temperature is 800 ℃, the pressure is normal, the flux of water is 0.6mL/min, and the gas composition at the outlet of the biological coke gasification reactor is H2The volume fraction is 57.3 percent, and the concentration of hydrogen in the gasified gas is further improved by a water-vapor shift reactorFrom the gas at the outlet of the water-gas shift reactor H2The volume fraction reaches 54.8 percent, the hydrogen concentration can be increased to 99 percent through pressure swing adsorption, and the biomass hydrogen production rate of the whole process is 41g of hydrogen/kg of biomass.
Claims (13)
1. A method for producing hydrogen from biomass, which comprises the following steps:
(1) the biomass raw material enters a carbonization reactor for reaction to obtain biological coke and volatile gas;
(2) and (2) uniformly mixing the biological coke obtained in the step (1) with a gasification catalyst, then feeding the mixture into a gasification reactor, contacting with steam for reaction, and further carrying out steam shift reaction and pressure swing adsorption treatment on the gasified gas obtained by the reaction to obtain a hydrogen product.
2. A method for producing hydrogen from biomass as claimed in claim 1 wherein the biomass feedstock is derived from any lignocellulose containing material, such as forestry residues or agricultural residues.
3. A method for producing hydrogen from biomass as claimed in claim 1 wherein the biomass feedstock has a maximum dimension in the direction of no more than 30mm, preferably 1 to 25 mm.
4. The biomass hydrogen production method according to claim 1, wherein the reaction temperature of the biomass raw material in the carbonization reactor in the step (1) is 200-550 ℃, preferably 250-450 ℃.
5. The biomass hydrogen production method according to claim 1, wherein the gasification catalyst in the step (2) comprises a component A and a component B, wherein the component A is an alkali metal halide, the component B is an alkaline earth metal sulfate or an alkaline earth metal carbonate, and the mass ratio of the component A to the component B is 30: 1-1: 5, preferably 6: 1-1: 1.
6. the biomass hydrogen production process according to claim 5, wherein the alkali element in the alkali halide is one or more of lithium, sodium, potassium, rubidium, cesium, francium; the halogen in the alkali metal halide is one or more of fluorine, chlorine, bromine and iodine, and further specifically, the alkali metal halide is selected from one or more of lithium chloride, sodium chloride, potassium chloride, rubidium chloride, cesium chloride, francium chloride, lithium fluoride, sodium fluoride, potassium fluoride, rubidium fluoride, cesium fluoride, francium fluoride, lithium bromide, sodium bromide, potassium bromide, rubidium bromide, cesium bromide, francium bromide, lithium iodide, sodium iodide, potassium iodide, rubidium iodide, cesium iodide and francium iodide, and preferably one or more of sodium chloride, potassium chloride, sodium bromide, potassium bromide, sodium iodide and potassium iodide.
7. The biomass hydrogen production method according to claim 5, wherein the alkaline earth metal sulfate is one or more of beryllium sulfate, magnesium sulfate, calcium sulfate, strontium sulfate, barium sulfate and radium sulfate, preferably one or more of magnesium sulfate, calcium sulfate and barium sulfate.
8. The biomass hydrogen production method according to claim 5, wherein the alkaline earth metal carbonate is one or more of beryllium carbonate, magnesium carbonate, calcium carbonate, strontium carbonate, barium carbonate and radium carbonate, preferably one or more of magnesium carbonate and calcium carbonate.
9. The biomass hydrogen production method according to claim 1, wherein the gasification reaction conditions in the step (2) are as follows: the reaction temperature is 700-950 ℃, preferably 750-900 ℃, and the flow rate of the water is 0.05-0.8 mL/min.
10. The biomass hydrogen production method according to claim 1, wherein the mass ratio of the biological coke gasification catalyst to the biomass raw material in the step (2) is 60-1: 99 to 40.
11. The biomass hydrogen production method according to claim 1, wherein the reaction conditions of the water-gas shift reaction device in the step (2) are as follows: the reaction temperature is 250-300 ℃, the volume ratio of the water vapor to the gasified gas is 0.5-0.9, and the space velocity of the gasified gas is 1500-2500 h-1。
12. The biomass hydrogen production method according to claim 1, wherein the operating conditions of the pressure swing adsorption device in the step (2) are as follows: the pressure is 1.5-4 MPa, and the temperature is 20-30 ℃.
13. A biomass hydrogen production system comprises
The carbonization reactor is used for receiving the biomass raw material and obtaining biological coke and volatile gas after treatment;
the gasification reactor is used for receiving the biological coke, the gasification catalyst and the water vapor from the carbonization reactor, and obtaining gasified gas after treatment;
the water-vapor shift reactor is used for receiving the gasified gas from the gasification reactor and obtaining hydrogen-containing body after treatment;
the pressure swing adsorption device is used for receiving the hydrogen-containing gas from the water-vapor shift reactor and obtaining a hydrogen product after treatment.
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