CN113913851B - Bipolar membrane electrolysis method for preparing carbon monoxide by electrolyzing carbon dioxide in organic electrolyte and simultaneously by-producing chlorine and metal hydroxide - Google Patents
Bipolar membrane electrolysis method for preparing carbon monoxide by electrolyzing carbon dioxide in organic electrolyte and simultaneously by-producing chlorine and metal hydroxide Download PDFInfo
- Publication number
- CN113913851B CN113913851B CN202111348680.2A CN202111348680A CN113913851B CN 113913851 B CN113913851 B CN 113913851B CN 202111348680 A CN202111348680 A CN 202111348680A CN 113913851 B CN113913851 B CN 113913851B
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- Prior art keywords
- chamber
- carbon dioxide
- electrolyte
- anode
- cathode
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 296
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 148
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 148
- 239000012528 membrane Substances 0.000 title claims abstract description 124
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 90
- 229910002091 carbon monoxide Inorganic materials 0.000 title claims abstract description 90
- 239000000460 chlorine Substances 0.000 title claims abstract description 69
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 239000005486 organic electrolyte Substances 0.000 title claims abstract description 51
- 238000005868 electrolysis reaction Methods 0.000 title claims abstract description 48
- 229910000000 metal hydroxide Inorganic materials 0.000 title claims abstract description 40
- 150000004692 metal hydroxides Chemical class 0.000 title claims abstract description 40
- 229910001902 chlorine oxide Inorganic materials 0.000 title claims abstract description 26
- 239000003792 electrolyte Substances 0.000 claims abstract description 109
- 239000002131 composite material Substances 0.000 claims abstract description 84
- 238000005341 cation exchange Methods 0.000 claims abstract description 42
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 37
- 238000000034 method Methods 0.000 claims abstract description 33
- 238000006243 chemical reaction Methods 0.000 claims abstract description 32
- 239000007864 aqueous solution Substances 0.000 claims abstract description 31
- 239000006227 byproduct Substances 0.000 claims abstract description 16
- 229910001510 metal chloride Inorganic materials 0.000 claims abstract description 14
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000000126 substance Substances 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 67
- -1 chlorine ions Chemical class 0.000 claims description 50
- 150000001450 anions Chemical class 0.000 claims description 49
- 150000001768 cations Chemical class 0.000 claims description 43
- 239000007789 gas Substances 0.000 claims description 42
- 239000000243 solution Substances 0.000 claims description 34
- 230000007062 hydrolysis Effects 0.000 claims description 30
- 238000006460 hydrolysis reaction Methods 0.000 claims description 30
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 30
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 26
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 26
- 238000010521 absorption reaction Methods 0.000 claims description 25
- 239000001257 hydrogen Substances 0.000 claims description 17
- 229910052739 hydrogen Inorganic materials 0.000 claims description 17
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 16
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 15
- 238000007254 oxidation reaction Methods 0.000 claims description 15
- 239000003054 catalyst Substances 0.000 claims description 14
- 238000010494 dissociation reaction Methods 0.000 claims description 13
- 230000005593 dissociations Effects 0.000 claims description 13
- 239000010411 electrocatalyst Substances 0.000 claims description 13
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 claims description 13
- 239000011780 sodium chloride Substances 0.000 claims description 13
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 12
- 238000003860 storage Methods 0.000 claims description 12
- 239000004696 Poly ether ether ketone Substances 0.000 claims description 11
- 239000004698 Polyethylene Substances 0.000 claims description 11
- HTXDPTMKBJXEOW-UHFFFAOYSA-N dioxoiridium Chemical compound O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 claims description 11
- 229920002530 polyetherether ketone Polymers 0.000 claims description 11
- 229920000573 polyethylene Polymers 0.000 claims description 11
- 239000002033 PVDF binder Substances 0.000 claims description 10
- 239000002608 ionic liquid Substances 0.000 claims description 10
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 9
- 239000003115 supporting electrolyte Substances 0.000 claims description 9
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 8
- 239000001103 potassium chloride Substances 0.000 claims description 8
- 235000011164 potassium chloride Nutrition 0.000 claims description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 7
- 230000001502 supplementing effect Effects 0.000 claims description 7
- 239000010936 titanium Substances 0.000 claims description 7
- 229910052719 titanium Inorganic materials 0.000 claims description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 229920001577 copolymer Polymers 0.000 claims description 6
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 claims description 6
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 229910001507 metal halide Inorganic materials 0.000 claims description 6
- 229920001467 poly(styrenesulfonates) Polymers 0.000 claims description 6
- 229920002554 vinyl polymer Polymers 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 5
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 5
- 239000011248 coating agent Substances 0.000 claims description 5
- 238000000576 coating method Methods 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- 229910000457 iridium oxide Inorganic materials 0.000 claims description 5
- 229920005548 perfluoropolymer Polymers 0.000 claims description 5
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- 150000003335 secondary amines Chemical group 0.000 claims description 5
- 150000003460 sulfonic acids Chemical class 0.000 claims description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 4
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 4
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 4
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- WGLPBDUCMAPZCE-UHFFFAOYSA-N chromium trioxide Inorganic materials O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 3
- VQWFNAGFNGABOH-UHFFFAOYSA-K chromium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[Cr+3] VQWFNAGFNGABOH-UHFFFAOYSA-K 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 3
- 229960004887 ferric hydroxide Drugs 0.000 claims description 3
- 229920002681 hypalon Polymers 0.000 claims description 3
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 claims description 3
- 229910021645 metal ion Inorganic materials 0.000 claims description 3
- 229920002492 poly(sulfone) Polymers 0.000 claims description 3
- 229920013636 polyphenyl ether polymer Polymers 0.000 claims description 3
- 239000004800 polyvinyl chloride Substances 0.000 claims description 3
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-O pyridinium Chemical compound C1=CC=[NH+]C=C1 JUJWROOIHBZHMG-UHFFFAOYSA-O 0.000 claims description 3
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 3
- 229910001887 tin oxide Inorganic materials 0.000 claims description 3
- 239000004408 titanium dioxide Substances 0.000 claims description 3
- 239000001763 2-hydroxyethyl(trimethyl)azanium Substances 0.000 claims description 2
- 235000019743 Choline chloride Nutrition 0.000 claims description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 2
- 239000005977 Ethylene Substances 0.000 claims description 2
- VJFCXDHFYISGTE-UHFFFAOYSA-N O=[Co](=O)=O Chemical compound O=[Co](=O)=O VJFCXDHFYISGTE-UHFFFAOYSA-N 0.000 claims description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- 229910000323 aluminium silicate Inorganic materials 0.000 claims description 2
- 150000001412 amines Chemical group 0.000 claims description 2
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 claims description 2
- 229910001626 barium chloride Inorganic materials 0.000 claims description 2
- 229940073608 benzyl chloride Drugs 0.000 claims description 2
- 229910052797 bismuth Inorganic materials 0.000 claims description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 2
- SGMZJAMFUVOLNK-UHFFFAOYSA-M choline chloride Chemical compound [Cl-].C[N+](C)(C)CCO SGMZJAMFUVOLNK-UHFFFAOYSA-M 0.000 claims description 2
- 229960003178 choline chloride Drugs 0.000 claims description 2
- 229940117975 chromium trioxide Drugs 0.000 claims description 2
- GAMDZJFZMJECOS-UHFFFAOYSA-N chromium(6+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Cr+6] GAMDZJFZMJECOS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 150000004985 diamines Chemical class 0.000 claims description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 2
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052741 iridium Inorganic materials 0.000 claims description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 2
- 239000012046 mixed solvent Substances 0.000 claims description 2
- 229910052762 osmium Inorganic materials 0.000 claims description 2
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 claims description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- 239000010948 rhodium Substances 0.000 claims description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 2
- 229910045601 alloy Inorganic materials 0.000 claims 1
- 239000000956 alloy Substances 0.000 claims 1
- 150000002739 metals Chemical class 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 24
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 12
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 8
- 239000002105 nanoparticle Substances 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 5
- 229910001863 barium hydroxide Inorganic materials 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 229910001316 Ag alloy Inorganic materials 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- 229910021397 glassy carbon Inorganic materials 0.000 description 4
- 150000002430 hydrocarbons Chemical group 0.000 description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 4
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910001297 Zn alloy Inorganic materials 0.000 description 3
- 229910003481 amorphous carbon Inorganic materials 0.000 description 3
- 229910001422 barium ion Inorganic materials 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- 125000001453 quaternary ammonium group Chemical group 0.000 description 3
- 229910001415 sodium ion Inorganic materials 0.000 description 3
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 3
- DPKBAXPHAYBPRL-UHFFFAOYSA-M tetrabutylazanium;iodide Chemical compound [I-].CCCC[N+](CCCC)(CCCC)CCCC DPKBAXPHAYBPRL-UHFFFAOYSA-M 0.000 description 3
- 229910001020 Au alloy Inorganic materials 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003034 coal gas Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 238000004070 electrodeposition Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910001414 potassium ion Inorganic materials 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- KBLZDCFTQSIIOH-UHFFFAOYSA-M tetrabutylazanium;perchlorate Chemical compound [O-]Cl(=O)(=O)=O.CCCC[N+](CCCC)(CCCC)CCCC KBLZDCFTQSIIOH-UHFFFAOYSA-M 0.000 description 2
- 229910020366 ClO 4 Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- DGXKDBWJDQHNCI-UHFFFAOYSA-N dioxido(oxo)titanium nickel(2+) Chemical compound [Ni++].[O-][Ti]([O-])=O DGXKDBWJDQHNCI-UHFFFAOYSA-N 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- PQTCMBYFWMFIGM-UHFFFAOYSA-N gold silver Chemical compound [Ag].[Au] PQTCMBYFWMFIGM-UHFFFAOYSA-N 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/23—Carbon monoxide or syngas
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/34—Simultaneous production of alkali metal hydroxides and chlorine, oxyacids or salts of chlorine, e.g. by chlor-alkali electrolysis
- C25B1/46—Simultaneous production of alkali metal hydroxides and chlorine, oxyacids or salts of chlorine, e.g. by chlor-alkali electrolysis in diaphragm cells
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
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Abstract
The invention relates to a bipolar membrane electrolysis method for preparing carbon monoxide by electrolyzing carbon dioxide in an organic electrolyte and simultaneously preparing by-products of chlorine and metal hydroxide, belonging to the technical field of phosgene chemical industry. The bipolar membrane and the cation exchange membrane are used for dividing the electrolytic cell into a cathode chamber, an intermediate chamber and an anode chamber to form a three-compartment electrolytic cell, the electrolyte in the cathode chamber is an organic composite electrolyte dissolved with a large amount of carbon dioxide, the electrolyte in the intermediate chamber is a metal hydroxide aqueous solution, the electrolyte in the anode chamber is a metal chloride aqueous solution, carbon monoxide is generated on the cathode and chlorine is generated on the anode in the electrolytic reaction process, and the content of the metal hydroxide in the intermediate chamber is increased. The method provided by the invention can synchronously produce carbon monoxide, chlorine and metal hydroxide under the conditions of normal temperature and normal pressure, and has the advantages of short process flow, simple operation method, low production cost, small occupied area of equipment, easiness in starting and stopping, greenness, no pollution and the like.
Description
Technical Field
The invention relates to a bipolar membrane electrolysis method for preparing carbon monoxide by electrolyzing carbon dioxide in an organic electrolyte, and simultaneously preparing by-products of chlorine and metal hydroxide, belonging to the technical field of phosgene chemical industry.
Background
Phosgene is an important acylating agent and can be used for preparing high-added-value products such as medicines, pesticides, dyes and the like. Currently, phosgene (CO+Cl) is industrially produced mainly by using carbon monoxide and chlorine as raw materials 2 =COCl 2 ) The method has the defects of long process flow, large equipment occupation area, complex operation method, high production cost and the like.
The electroreduction of carbon dioxide to carbon monoxide, the synthesis of downstream products (including phosgene), is one of the important technological approaches to realize the recycling of carbon resources. The traditional method mainly comprises the steps of electrically reducing carbon dioxide into carbon monoxide in an aqueous solution, wherein an anode reaction is an oxidation reaction of water, and a product is oxygen. The method has a research history of over 100 years, has not been applied to industrialization so far, and has the main problems that: first, carbon dioxide is a nonpolar molecule, has very small solubility in aqueous solution, and only 0.033mol/L under standard conditions, so that the current density of the cathode reaction is too low; secondly, when carbon monoxide is prepared by electrolyzing carbon dioxide in aqueous solution, in order to improve the conductivity of the electrolyte, an inorganic supporting electrolyte is required to be added into the electrolyte, so that some inorganic impurities are inevitably brought into the electrolyte, wherein some impurities undergo electrodeposition reaction on the surface of a cathode to form surface active points with low hydrogen evolution overpotential, so that the speed of the hydrogen evolution reaction is increased, and the electrocatalytic activity of an electrode material on the carbon dioxide electroreduction reaction is reduced; thirdly, when carbon dioxide is electrolyzed in an aqueous solution to prepare carbon monoxide, a small amount of carbon dioxide is deeply reduced due to a specific electrode/electrolyte interface environment to generate amorphous carbon which is attached to the surface of a cathode, so that the current efficiency of generating the carbon monoxide is rapidly reduced to zero; fourth, the cathode reaction product is carbon monoxide and the anode reaction product is oxygen, and the carbon monoxide can be prepared from coal gas, the oxygen can be prepared from air separation, and the production cost of the latter two methods is very low, so that the production cost of carbon monoxide prepared by carbon dioxide electrolysis is too high, and the method is not economically viable.
Disclosure of Invention
In order to solve the problems and the defects of the prior art, the invention provides a bipolar membrane electrolysis method for preparing carbon monoxide by electrolyzing carbon dioxide in an organic electrolyte and simultaneously preparing by-products of chlorine and metal hydroxide. The invention is realized by the following technical scheme.
The bipolar membrane and the cation exchange membrane are used for dividing the electrolytic cell into a cathode chamber, an intermediate chamber and an anode chamber to form a three-compartment electrolytic cell, the electrolyte in the cathode chamber is an organic composite electrolyte dissolved with a large amount of carbon dioxide, the electrolyte in the intermediate chamber is a metal hydroxide aqueous solution, the electrolyte in the anode chamber is a metal chloride aqueous solution, carbon monoxide is generated on the cathode and chlorine is generated on the anode in the electrolytic reaction process, and the content of the metal hydroxide in the intermediate chamber is increased.
The anion permeable layer in the bipolar membrane is one of an imidazole polyether ether ketone anion permeable layer, a styrene/ethylene benzyl chloride copolymer anion permeable layer containing diamine, a quaternized polyethylene anion permeable layer, a quaternized polyvinyl chloride anion permeable layer, a quaternized polyphenyl ether anion permeable layer, a polysulfone anion permeable layer containing bicyclic amine, a quaternized styrene/divinylbenzene copolymer anion permeable layer and a perfluoropolymer anion permeable layer containing quaternary amine and secondary amine, and the thickness of the anion permeable layer is 15-300 micrometers; the cation permeation layer in the bipolar membrane is one of a sulfonated polyethylene cation permeation layer, a sulfonated polystyrene cation permeation layer, a sulfonated polyether-ether-ketone cation permeation layer, a sulfonated polyvinylidene fluoride cation permeation layer and a perfluorinated sulfonic acid type cation permeation layer, the thickness is 15-300 microns, and a water dissociation catalyst is introduced into the interface area of the cation permeation layer and the anion permeation layer, wherein the water dissociation catalyst is one or a mixture of any proportion of a plurality of polyvinyl acid/polyvinyl pyridinium complex, sulfonated polyether-ether-ketone, chromium hydroxide, zirconium oxide, aluminosilicate, chromium trioxide, nickel oxide, aluminum hydroxide, tin oxide, ferric hydroxide, manganese dioxide, iridium dioxide, titanium dioxide, silicon dioxide, indium trioxide, cobalt trioxide, bismuth, tin, ruthenium, rhodium, palladium, osmium, iridium and platinum.
The cation exchange membrane is one of a sulfonated polyethylene cation exchange membrane, a sulfonated polystyrene cation exchange membrane, a sulfonated polyvinylidene fluoride cation exchange membrane, a chlorosulfonated polyethylene cation exchange membrane and a perfluorosulfonic acid cation exchange membrane.
The organic composite electrolyte in the cathode chamber electrolyte comprises three functional components: the organic solvent is one of dimethyl sulfoxide, N-dimethylformamide, propylene carbonate, N-methylpyrrolidone, diethyl carbonate and acetonitrile or a mixed solvent formed by the solvents according to any proportion, the organic supporting electrolyte is one of quaternary ammonium salt and choline chloride or a mixture of the two supporting electrolytes according to any proportion, and the homogeneous electrocatalyst is one of metalloporphyrin compound, metal phthalocyanine compound, tricarbonyl-2, 2' -bipyridine metal halide, imidazole ionic liquid and pyridine ionic liquid or a mixture formed by the homogeneous electrocatalyst according to any proportion.
The quaternary ammonium salt as the organic supporting electrolyte in the organic composite electrolyte has the chemical structural formula:
R 1 、R 2 、R 3 、R 4 Is C 1 -C 5 Hydrocarbon chain of X - Is CF (CF) 3 SO 3 - 、ClO 4 - 、(CF 3 SO 2 ) 2 N - 、CF 3 COO - 、H 2 PO 4 - 、HCO 3 - 、Cl - 、HSO 4 - 、Br - 、I - Any one of the following.
Metalloporphyrin compound as homogeneous electrocatalyst in organic composite electrolyte, its chemical structural formula is:
M 1 is any one of iron, cobalt and nickel, R 1 、R 2 、R 3 、R 4 Is a hydrogen atom or C 1 -C 5 Or a benzene substituent.
The metal phthalocyanine compound used as the homogeneous electrocatalyst in the organic composite electrolyte has the chemical structural formula as follows:
M 2 iron, manganese, copper or nickel.
Tricarbonyl-2, 2' -bipyridine metal halides as organic homogeneous electrocatalysts in organic composite electrolytes have the chemical structural formula:
M 3 is manganese or rhenium, X is Cl, br or I, R 1 、R 2 Is a hydrogen atom or C 1 -C 5 Is a hydrocarbon chain of (2).
The imidazole ionic liquid used as the homogeneous electrocatalyst in the organic composite electrolyte has the chemical structural formula:
R 1 、R 2 is C 1 -C 5 Is a hydrocarbon chain of (2); m, N is connected toA hydrogen atom or a functional group on a hydrocarbon chain, the functional group being: -CN, -NH 2 or-OH; x is X - For (CF) 3 SO 2 ) 2 N - 、CF 3 COO - 、CF 3 SO 3 - 、HCO 3 - 、HSO 4 - 、H 2 PO 4 - 、Br - 、Cl - Any one of the following.
The structural formula of the pyridine ionic liquid serving as the homogeneous electrocatalyst in the organic composite electrolyte is as follows:
wherein R is C 1 -C 5 M is a functional group or a hydrogen atom attached to the hydrocarbon chain, the functional group being: -NH 2 -CN or-OH; x is X - Is CF (CF) 3 SO 3 - 、CF 3 COO - 、(CF 3 SO 2 ) 2 N - 、HCO 3 - 、H 2 PO 4 - 、HSO 4 - 、Cl - 、Br - 、I - Any one of the following.
The anode of the three-compartment electrolytic cell is an iridium oxide coating titanium electrode and IrO 2 ·Ta 2 O 5 The anode chamber electrolyte is a metal chloride aqueous solution, and is a mixture aqueous solution formed by one or any proportion of sodium chloride, potassium chloride, lithium chloride and barium chloride.
As shown in fig. 1, the specific operation steps are as follows:
dividing an electrolytic cell into a cathode chamber, an intermediate chamber and an anode chamber by using a bipolar membrane 4 and a cation exchange membrane 6 to form a three-compartment electrolytic cell, respectively placing a cathode 2 and an anode 8 in the cathode chamber and the anode chamber, and adding water (intermediate chamber electrolyte 5) into the intermediate chamber;
dissolving an organic supporting electrolyte into an organic solvent to prepare an organic electrolyte with the concentration of 0.1-4.0 mol/L, adding a homogeneous electrocatalyst into the obtained organic electrolyte to enable the concentration of the homogeneous electrocatalyst to reach 0.01-0.4 mol/L, obtaining an organic composite electrolyte, and preparing a metal chloride aqueous solution (anode electrolyte 7) with the mass percent concentration of 10% -25%;
dissolving carbon dioxide into an organic composite electrolyte (catholyte 3) in a gas absorption tower 1, continuously injecting the organic composite electrolyte containing a large amount of carbon dioxide into the bottom of a cathode chamber, flowing the organic composite electrolyte containing lower concentration carbon dioxide at the upper part of the cathode chamber out of the upper part of the cathode chamber, and sending the organic composite electrolyte containing lower concentration carbon dioxide into the gas absorption tower 1 again for dissolving and absorbing carbon dioxide, wherein the obtained organic composite electrolyte containing a large amount of carbon dioxide is injected into the bottom of the cathode chamber of the three-compartment electrolytic cell again, so that catholyte circulation is formed; continuously injecting metal chloride aqueous solution into the anode chamber, enabling the aqueous solution containing the metal chloride with lower concentration at the upper part of the anode chamber to flow out of the upper part of the anode chamber, supplementing the metal chloride and water, then injecting the solution into the anode chamber, continuously injecting water into the middle chamber, and evaporating and separating the solution flowing out of the middle chamber to obtain metal hydroxide;
Step four, switching on an electrolysis power supply at normal temperature and normal pressure, controlling the voltage of a tank to be 5.2-9.6V, and enabling chloride ions in an anode chamber to undergo oxidation reaction on an anode to generate chlorine; the metal ions in the anode chamber pass through the cation exchange membrane and enter the middle chamber to meet hydroxide ions generated by the hydrolysis and dissociation of the bipolar membrane, so as to generate metal hydroxide; the carbon dioxide is subjected to electroreduction reaction on the cathode to generate carbon monoxide and carbonate, the carbonate reacts with hydrogen ions generated by the hydrolysis of the bipolar membrane to generate carbon dioxide and water, and the generated carbon monoxide and chlorine are respectively stored in the gas storage tank.
The chlorine gas generated by the anode reaction and the carbon monoxide generated by the cathode reaction can be independently used as chemical raw materials, and can be mixed for producing phosgene, and the solution flowing out of the middle chamber is evaporated and separated to obtain metal hydroxide.
The beneficial effects of the invention are as follows:
(1) At present, the industrial production mainly adopts carbon monoxide and chlorine as raw materials to produce phosgene (CO+Cl) 2 =COCl 2 ) The method has the advantages of short process flow, simple operation method, low production cost, small occupied area of equipment, easy start and stop, greenness, no pollution and the like.
(2) The electroreduction of carbon dioxide to carbon monoxide, the synthesis of downstream products (including phosgene), is one of the important technological approaches to realize the recycling of carbon resources. In the traditional method, carbon dioxide is electrolyzed in aqueous solution to prepare carbon monoxide, the anode reaction is oxidation reaction of water, and the product is oxygen. The method has a research history of over 100 years, and cannot realize industrial application until now, and has the main problems that: firstly, carbon dioxide is a nonpolar molecule, the solubility in aqueous solution is very small, and only 0.033mol/L is required in a standard state, so that the current density of cathode reaction is too low, and the carbon dioxide is electrically reduced into carbon monoxide by utilizing a gas diffusion electrode, so that the key technical barriers of the traditional technology cannot be fundamentally solved due to the reasons of electrode flooding, electrode salt formation, electrode inactivation and the like; secondly, when carbon monoxide is prepared by electrolyzing carbon dioxide in aqueous solution, in order to improve the conductivity of the electrolyte, inorganic supporting electrolyte is added into the electrolyte, so that some inorganic impurities are inevitably brought into the electrolyte, wherein some impurities generate electrodeposition reaction on the surface of a cathode to form surface active points with low hydrogen evolution overpotential, so that the speed of the hydrogen evolution reaction of the cathode is increased, and meanwhile, the catalytic activity of an electrode material on the carbon dioxide electroreduction reaction is reduced; thirdly, when carbon dioxide is electrolyzed in an aqueous solution to prepare carbon monoxide, a small amount of carbon dioxide is deeply reduced due to a specific electrode/electrolyte interface environment to generate amorphous carbon, and the amorphous carbon is attached to the surface of a cathode, so that the cathode is poisoned, and the current efficiency for generating the carbon monoxide is rapidly reduced to zero; fourth, the cathode reaction product is carbon monoxide and the anode reaction product is oxygen, and the carbon monoxide can be prepared from coal gas, the oxygen can be prepared from air separation, and the production cost of the latter two methods is very low, so that the production cost of carbon monoxide prepared by carbon dioxide electrolysis is too high, and the method is not economically viable.
The method provided by the invention can electrolyze carbon dioxide in organic electrolyte to prepare carbon monoxide, and simultaneously byproducts chlorine and metal hydroxide, and compared with the traditional method for preparing carbon monoxide by electrolyzing carbon dioxide, the method provided by the invention has the following advantages: first, carbon dioxide is a nonpolar molecule and has good solubility in organic electrolyte, so that the current density and current efficiency of the reaction can be improved by electrolyzing carbon dioxide to prepare carbon monoxide in the organic electrolyte; the second, organic electrolyte is totally different from the aqueous solution in composition, so, the electrode deactivation problem caused by electrolyte impurity is solved; thirdly, carbon monoxide is prepared by electrolyzing carbon dioxide in an organic electrolyte, and the problem of electrode poisoning is solved because the structure of an electric double layer on the surface of an electrode is fundamentally changed; fourth, the bipolar membrane electrolytic method provided by the invention can be used for electrically reducing carbon dioxide into carbon monoxide, and simultaneously byproducts of chlorine and metal hydroxide, wherein the obtained carbon monoxide and the obtained chlorine can be used for producing phosgene, and can also be independently used as chemical raw materials, and the obtained metal hydroxide is an important basic chemical raw material, so that the additional value of the product can be greatly improved by using the method provided by the patent. Fifth, the method provided by the invention can continuously and stably electrolyze carbon dioxide to prepare carbon monoxide through the circulation of the catholyte; sixth, the bipolar membrane electrolytic cell provided by the invention can improve the efficiency and yield of electrolytic reaction by increasing the number of the repeated units of the electrolytic cell and enlarging the electrode area.
Drawings
FIG. 1 is a schematic view of the structure of an electrolytic cell of the present invention.
FIG. 2 is a schematic view of an electrolytic cell according to example 1 of the present invention.
In the figure: 1-gas absorption tower, 2-cathode, 3-catholyte, 4-bipolar membrane, 5-intermediate chamber electrolyte, 6-cation exchange membrane, 7-anolyte and 8-anode.
Detailed Description
The invention will be further described with reference to the drawings and detailed description.
Example 1
A bipolar membrane electrolysis method for preparing carbon monoxide by electrolyzing carbon dioxide in an organic electrolyte and simultaneously preparing chlorine and metal hydroxide as byproducts comprises the following specific operation steps:
the first step is to divide the electrolytic cell into a cathode chamber, an intermediate chamber and an anode chamber by using a bipolar membrane and a perfluorinated sulfonic acid type cation exchange membrane, wherein an Au electrode is arranged in the cathode chamber as a cathode, an iridium oxide coating titanium electrode is arranged in the anode chamber as an anode, and water is added in the intermediate chamber. The anion permeation layer of the bipolar membrane is an imidazole polyether ether ketone anion permeation layer with the thickness of 200 microns, the cation permeation layer is a perfluorinated sulfonic acid cation permeation layer with the thickness of 150 microns, and titanium oxide/nickel oxide nano particles are introduced into the interface area of the cation permeation layer and the anion permeation layer to serve as a water dissociation catalyst.
Dissolving tetrabutylammonium perchlorate into propylene carbonate to obtain an organic electrolyte with the concentration of 0.1mol/L, and adding an iron porphyrin compound into the organic electrolyte to obtain an organic composite electrolyte with the concentration of 0.01 mol/L;
dissolving and absorbing carbon dioxide by using an organic composite electrolyte in a gas absorption tower, continuously injecting the organic composite electrolyte containing a large amount of carbon dioxide into the bottom of a cathode chamber, flowing the organic composite electrolyte containing lower concentration carbon dioxide at the upper part of the cathode chamber out of the upper part of the cathode chamber, reintroducing the organic composite electrolyte containing lower concentration carbon dioxide into the gas absorption tower for dissolving and absorbing carbon dioxide, and injecting the obtained organic composite electrolyte containing a large amount of carbon dioxide into the bottom of the cathode chamber of the three-compartment electrolytic cell again, thereby forming a catholyte cycle; continuously injecting 25wt% NaCl water solution into the anode chamber, flowing water solution containing lower concentration NaCl from the upper part of the anode chamber, replenishing NaCl and water, and injecting into the anode chamber again; water is continuously injected into the middle chamber, and the solution flowing out of the middle chamber is evaporated and separated to obtain sodium hydroxide.
And fourthly, switching on an electrolysis power supply at normal temperature and normal pressure, controlling the voltage of a tank to be 5.2V, enabling chloride ions to undergo oxidation reaction on an anode to generate chlorine, enabling sodium ions in an anode chamber to pass through a cation exchange membrane and enter an intermediate chamber to meet hydroxide ions generated by hydrolysis of a bipolar membrane to generate sodium hydroxide, enabling carbon dioxide to undergo electroreduction reaction on a cathode to generate carbon monoxide and carbonate, and enabling carbonate to react with hydrogen ions generated by hydrolysis of the bipolar membrane to generate carbon dioxide and water. The result of the electrolysis experiment for the period of 12 hours shows that the current efficiency of generating carbon monoxide is stabilized at 92 percent, and the current density is stabilized at 30mA/cm 2 The current efficiency of the generated chlorine gas is stabilized at 96%, and the current density is stabilized at 25mA/cm 2 The generated carbon monoxide and chlorine are respectively stored in a gas storage tank.
In this embodiment, as shown in fig. 2, the gas generated in the cathode chamber is detected as CO gas by gas chromatography, the solution in the middle chamber is tested by using pH test paper to indicate that sodium hydroxide solution is generated, and the gas generated in the anode chamber is tested by using starch potassium iodide test paper to indicate that the gas is Cl 2 。
Example 2
A bipolar membrane electrolysis method for preparing carbon monoxide by electrolyzing carbon dioxide in an organic electrolyte and simultaneously preparing chlorine and metal hydroxide as byproducts comprises the following specific operation steps:
Dividing an electrolytic cell into a cathode chamber, an intermediate chamber and an anode chamber by using a bipolar membrane and a sulfonated polyethylene cation exchange membrane, placing an Ag electrode as a cathode in the cathode chamber and placing IrO in the anode chamber 2 ·Ta 2 O 5 The coated titanium electrode served as the anode and water was added to the intermediate chamber. The anion permeation layer of the bipolar membrane is styrene/vinylbenzyl chloride copolymer anion permeation layer seed permeation containing diamineThe permeable layer has a thickness of 180 micrometers, the cation permeable layer is a sulfonated polyethylene cation permeable layer, the thickness is 250 micrometers, and a polyvinyl acid/polyvinyl pyridinium complex is introduced into the interface area of the cation permeable layer and the anion permeable layer to serve as a hydrolysis catalyst.
Dissolving tetrabutylammonium chloride into N-methylpyrrolidone to obtain 0.7mol/L organic composite electrolyte, and adding an iron phthalocyanine compound into the organic electrolyte to ensure that the concentration of the iron phthalocyanine compound reaches 0.02mol/L to obtain the organic composite electrolyte;
dissolving and absorbing carbon dioxide by using an organic composite electrolyte in a gas absorption tower, continuously injecting the organic composite electrolyte containing a large amount of carbon dioxide into the bottom of a cathode chamber, flowing the organic composite electrolyte containing lower concentration carbon dioxide at the upper part of the cathode chamber out of the upper part of the cathode chamber, reintroducing the organic composite electrolyte containing lower concentration carbon dioxide into the gas absorption tower for dissolving and absorbing carbon dioxide, and injecting the obtained organic composite electrolyte containing a large amount of carbon dioxide into the bottom of the cathode chamber of the three-compartment electrolytic cell again, thereby forming a catholyte cycle; continuously injecting 24wt% KCl solution into the anode chamber, and injecting the aqueous solution containing lower concentration KCl at the upper part of the anode chamber into the anode chamber again after the KCl and water are supplemented; water is continuously injected into the middle chamber, and the solution flowing out of the middle chamber is evaporated and separated to obtain potassium hydroxide.
Step four, switching on an electrolysis power supply at normal temperature and normal pressure, controlling the voltage of a tank to be 6.8V, enabling chloride ions to undergo oxidation reaction on an anode to generate chlorine, enabling potassium ions in an anode chamber to pass through a cation exchange membrane and enter an intermediate chamber to meet hydroxide ions generated by hydrolysis of a bipolar membrane to generate potassium hydroxide, enabling carbon dioxide to undergo electroreduction reaction on a cathode to generate carbon monoxide and carbonate, and enabling carbonate to react with hydrogen ions generated by hydrolysis of the bipolar membrane to generate carbon dioxide and water. The result of the electrolysis experiment for the period of 12 hours shows that the current efficiency of generating carbon monoxide is stabilized at 93 percent, and the current density is stabilized at 39mA/cm 2 The current efficiency of chlorine generation was stabilized at 95% and the current density was stabilized at 32mA/cm 2 The generated carbon monoxide and chlorine are respectively stored in a gas storage tank.
Example 3
A bipolar membrane electrolysis method for preparing carbon monoxide by electrolyzing carbon dioxide in an organic electrolyte and simultaneously preparing chlorine and metal hydroxide as byproducts comprises the following specific operation steps:
the method comprises the steps of firstly, dividing an electrolytic cell into a cathode chamber, an intermediate chamber and an anode chamber by using a bipolar membrane and a sulfonated polystyrene cation exchange membrane, placing a Zn electrode in the cathode chamber as a cathode, placing a glassy carbon electrode in the anode chamber as an anode, and adding water in the intermediate chamber. The anion permeation layer of the bipolar membrane is a quaternized polyvinyl chloride anion permeation layer, the thickness is 210 microns, the cation permeation layer is a sulfonated polyvinylidene fluoride cation permeation layer, the thickness is 150 microns, and sulfonated polyether-ether-ketone is introduced into the interface area of the cation permeation layer and the anion permeation layer to serve as a hydrolysis catalyst.
Dissolving tetrabutylammonium bromide into N-methylpyrrolidone to obtain an organic electrolyte with the concentration of 0.6mol/L, and adding tricarbonyl-2, 2 '-bipyridine metal halide into the organic electrolyte to enable the concentration of the tricarbonyl-2, 2' -bipyridine metal halide to reach 0.2mol/L to obtain an organic composite electrolyte;
dissolving and absorbing carbon dioxide by using an organic composite electrolyte in a gas absorption tower, continuously injecting the organic composite electrolyte containing a large amount of carbon dioxide into the bottom of a cathode chamber, flowing the organic composite electrolyte containing lower concentration carbon dioxide at the upper part of the cathode chamber out of the upper part of the cathode chamber, reintroducing the organic composite electrolyte containing lower concentration carbon dioxide into the gas absorption tower for dissolving and absorbing carbon dioxide, and injecting the obtained organic composite electrolyte containing a large amount of carbon dioxide into the bottom of the cathode chamber of the three-compartment electrolytic cell again, thereby forming a catholyte cycle; continuously injecting 10wt% LiCl solution into the anode chamber, flowing out the aqueous solution containing low concentration LiCl at the upper part of the anode chamber, supplementing LiCl and water, and then injecting into the anode chamber again; water is continuously injected into the middle chamber, and the solution flowing out of the middle chamber is evaporated and separated to obtain lithium hydroxide.
And fourthly, switching on an electrolysis power supply at normal temperature and normal pressure, controlling the cell voltage to be 8.6V, enabling chloride ions to undergo oxidation reaction on an anode to generate chlorine, enabling lithium ions in an anode chamber to pass through a cation exchange membrane and enter an intermediate chamber to meet hydroxide ions generated by hydrolysis of a bipolar membrane to generate lithium hydroxide, enabling carbon dioxide to undergo electroreduction reaction on a cathode to generate carbon monoxide and carbonate, and enabling carbonate to react with hydrogen ions generated by hydrolysis of the bipolar membrane to generate carbon dioxide and water. The result of the electrolysis experiment for the period of 12 hours shows that the current efficiency of generating carbon monoxide is stabilized at 91 percent, and the current density is stabilized at 56mA/cm 2 The current efficiency of the generated chlorine gas is stabilized at 95%, and the current density is stabilized at 47mA/cm 2 The generated carbon monoxide and chlorine are respectively stored in a gas storage tank.
Example 4
A bipolar membrane electrolysis method for preparing carbon monoxide by electrolyzing carbon dioxide in an organic electrolyte and simultaneously preparing chlorine and metal hydroxide as byproducts comprises the following specific operation steps:
the method comprises the steps of firstly, dividing an electrolytic cell into a cathode chamber, an intermediate chamber and an anode chamber by using a bipolar membrane and a sulfonated polyvinylidene fluoride cation exchange membrane, placing an Ag/Zn alloy electrode in the cathode chamber as a cathode, placing a graphite electrode in the anode chamber as an anode, and adding water in the intermediate chamber. The anion permeation layer of the bipolar membrane is a quaternized polyphenyl ether anion permeation layer, the thickness is 160 microns, the cation permeation layer is a sulfonated polyether-ether-ketone cation permeation layer, the thickness is 150 microns, and chromium hydroxide/zirconia nano particles are introduced into the interface area of the cation permeation layer and the anion permeation layer to serve as a hydrolysis catalyst.
Dissolving tetrabutylammonium perchlorate into diethyl carbonate to obtain 2mol/L organic electrolyte, and adding imidazole ionic liquid into the organic electrolyte to enable the concentration of the imidazole ionic liquid to reach 0.4mol/L to obtain organic composite electrolyte;
dissolving and absorbing carbon dioxide by using an organic composite electrolyte in a gas absorption tower, continuously injecting the organic composite electrolyte containing a large amount of carbon dioxide into the bottom of the cathode chamber at the upper part of the cathode chamberThe organic composite electrolyte containing the carbon dioxide with lower concentration flows out from the upper part of the cathode chamber, the organic composite electrolyte containing the carbon dioxide with lower concentration is reintroduced into the gas absorption tower for dissolving and absorbing the carbon dioxide, and the obtained organic composite electrolyte containing a large amount of carbon dioxide is reinjected into the bottom part of the cathode chamber of the three-compartment electrolytic cell, so that the catholyte circulation is formed; 15wt% BaCl was continuously injected into the anode chamber 2 Solution at the upper part of the anode chamber containing BaCl with lower concentration 2 The aqueous solution of (2) flows out from the upper part of the anode chamber and is supplemented with BaCl 2 And water, re-injecting into the anode chamber; water is continuously injected into the intermediate chamber, and the solution flowing out of the intermediate chamber is evaporated and separated to obtain barium hydroxide.
And fourthly, switching on an electrolysis power supply at normal temperature and normal pressure, controlling the cell voltage to be 5.9V, enabling chloride ions to undergo oxidation reaction on an anode to generate chlorine, enabling barium ions in an anode chamber to pass through a cation exchange membrane and enter an intermediate chamber to meet hydroxide ions generated by hydrolysis of a bipolar membrane to generate barium hydroxide, enabling carbon dioxide to undergo electroreduction reaction on a cathode to generate carbon monoxide and carbonate, and enabling carbonate to react with hydrogen ions generated by hydrolysis of the bipolar membrane to generate carbon dioxide and water. The experimental result of the electrolysis for 12 hours period shows that the current efficiency of generating carbon monoxide is stabilized at 94 percent, and the current density is stabilized at 24mA/cm 2 The current efficiency of the generated chlorine gas is stabilized at 96%, and the current density is stabilized at 21mA/cm 2 The generated carbon monoxide and chlorine are respectively stored in a gas storage tank.
Example 5
A bipolar membrane electrolysis method for preparing carbon monoxide by electrolyzing carbon dioxide in an organic electrolyte and simultaneously preparing chlorine and metal hydroxide as byproducts comprises the following specific operation steps:
the first step, the electrolytic cell is divided into a cathode chamber, an intermediate chamber and an anode chamber by a bipolar membrane and a chlorosulfonated polyethylene-based cation exchange membrane, a gold-silver alloy electrode is placed in the cathode chamber as a cathode, a glassy carbon electrode is placed in the anode chamber as an anode, and water is added in the intermediate chamber. The anion permeation layer of the bipolar membrane is a polysulfone anion permeation layer containing bicyclic amine, the thickness is 300 microns, the cation permeation layer is a sulfonated polyvinylidene fluoride cation permeation layer, the thickness is 15 microns, and chromium oxide/nickel oxide nano particles are introduced into the interface area of the cation permeation layer and the anion permeation layer to serve as a water dissociation catalyst.
Dissolving tetrabutyl ammonium chloride into dimethyl sulfoxide to obtain an organic electrolyte with the concentration of 4mol/L, and adding pyridine ionic liquid into the organic electrolyte to reach the concentration of 0.4mol/L to obtain an organic composite electrolyte;
dissolving and absorbing carbon dioxide by using an organic composite electrolyte in a gas absorption tower, continuously injecting the organic composite electrolyte containing a large amount of carbon dioxide into the bottom of a cathode chamber, flowing the organic composite electrolyte containing lower concentration carbon dioxide at the upper part of the cathode chamber out of the upper part of the cathode chamber, reintroducing the organic composite electrolyte containing lower concentration carbon dioxide into the gas absorption tower for dissolving and absorbing carbon dioxide, and injecting the obtained organic composite electrolyte containing a large amount of carbon dioxide into the bottom of the cathode chamber of the three-compartment electrolytic cell again, thereby forming a catholyte cycle; continuously injecting 22wt% NaCl solution into the anode chamber, allowing the water solution containing lower concentration NaCl at the upper part of the anode chamber to flow out from the upper part of the anode chamber, supplementing NaCl and water, and then injecting into the anode chamber again; water is continuously injected into the middle chamber, and the solution flowing out of the middle chamber is evaporated and separated to obtain sodium hydroxide.
And fourthly, switching on an electrolysis power supply at normal temperature and normal pressure, controlling the cell voltage to be 7.5V, enabling chloride ions to undergo oxidation reaction on an anode to generate chlorine, enabling sodium ions in an anode chamber to pass through a cation exchange membrane and enter an intermediate chamber to meet hydroxide ions generated by hydrolysis of a bipolar membrane to generate sodium hydroxide, enabling carbon dioxide to undergo electroreduction reaction on a cathode to generate carbon monoxide and carbonate, and enabling carbonate to react with hydrogen ions generated by hydrolysis of the bipolar membrane to generate carbon dioxide and water. The result of the electrolysis experiment for the period of 12 hours shows that the current efficiency of generating carbon monoxide is stabilized at 93 percent, and the current density is stabilized at 48mA/cm 2 The current efficiency of the generated chlorine gas is stabilized at 92%, and the current density is stabilized at 42mA/cm 2 The generated carbon monoxide and chlorine are respectively stored in a gas storage tank.
Example 6
A bipolar membrane electrolysis method for preparing carbon monoxide by electrolyzing carbon dioxide in an organic electrolyte and simultaneously preparing chlorine and metal hydroxide as byproducts comprises the following specific operation steps:
the first step, the electrolytic cell is divided into a cathode chamber, an intermediate chamber and an anode chamber by a bipolar membrane and a sulfonated polyethylene based cation exchange membrane, an Au/Ag alloy electrode is placed in the cathode chamber as a cathode, an iridium oxide coating titanium electrode is placed in the anode chamber as an anode, and water is added in the intermediate chamber. The anion permeation layer of the bipolar membrane is a quaternized styrene/divinylbenzene copolymer anion permeation layer, the thickness is 15 microns, the cation permeation layer is a sulfonated polyvinylidene fluoride cation permeation layer, the thickness is 300 microns, and aluminum hydroxide/tin oxide nano particles are introduced into the interface area of the cation permeation layer and the anion permeation layer to serve as a water dissociation catalyst.
Dissolving tetrabutylammonium bromide into N, N-dimethylformamide to obtain an organic electrolyte with the concentration of 3mol/L, and adding a metalloporphyrin compound into the organic electrolyte to enable the concentration of the metalloporphyrin compound to reach 0.02mol/L to obtain an organic composite electrolyte;
dissolving and absorbing carbon dioxide by using an organic composite electrolyte in a gas absorption tower, continuously injecting the organic composite electrolyte containing a large amount of carbon dioxide into the bottom of a cathode chamber, flowing the organic composite electrolyte containing lower concentration carbon dioxide at the upper part of the cathode chamber out of the upper part of the cathode chamber, reintroducing the organic composite electrolyte containing lower concentration carbon dioxide into the gas absorption tower for dissolving and absorbing carbon dioxide, and injecting the obtained organic composite electrolyte containing a large amount of carbon dioxide into the bottom of the cathode chamber of the three-compartment electrolytic cell again, thereby forming a catholyte cycle; 15wt% BaCl was continuously injected into the anode chamber 2 Solution at the upper part of the anode chamber containing BaCl with lower concentration 2 The aqueous solution of (2) flows out from the upper part of the anode chamber and is supplemented with BaCl 2 And water, re-injecting into the anode chamber; continuously injecting water into the intermediate chamber, evaporating the solution flowing from the intermediate chamber And (3) separating to obtain barium hydroxide.
And fourthly, switching on an electrolysis power supply at normal temperature and normal pressure, controlling the cell voltage to be 5.9V, enabling chloride ions to undergo oxidation reaction on an anode to generate chlorine, enabling barium ions in an anode chamber to pass through a cation exchange membrane and enter an intermediate chamber to meet hydroxide ions generated by hydrolysis of a bipolar membrane to generate barium hydroxide, enabling carbon dioxide to undergo electroreduction reaction on a cathode to generate carbon monoxide and carbonate, and enabling carbonate to react with hydrogen ions generated by hydrolysis of the bipolar membrane to generate carbon dioxide and water. The result of the electrolysis experiment for the period of 12 hours shows that the current efficiency of generating carbon monoxide is stabilized at 92 percent, and the current density is stabilized at 21mA/cm 2 The current efficiency of the generated chlorine gas is stabilized at 97%, and the current density is stabilized at 19mA/cm 2 The generated carbon monoxide and chlorine are respectively stored in a gas storage tank.
Example 7
A bipolar membrane electrolysis method for preparing carbon monoxide by electrolyzing carbon dioxide in an organic electrolyte and simultaneously preparing chlorine and metal hydroxide as byproducts comprises the following specific operation steps:
the first step is to divide the electrolytic cell into a cathode chamber, an intermediate chamber and an anode chamber by using a bipolar membrane and a perfluorinated sulfonic acid type cation exchange membrane, wherein an Au electrode is arranged in the cathode chamber as a cathode, an iridium oxide coating titanium electrode is arranged in the anode chamber as an anode, and water is added in the intermediate chamber. The anion permeation layer of the bipolar membrane is a perfluoropolymer anion permeation layer containing quaternary ammonium and secondary amine, the thickness is 200 micrometers, the cation permeation layer is a sulfonated polyvinylidene fluoride cation permeation layer, the thickness is 210 micrometers, and ferric hydroxide/manganese dioxide nano particles are introduced into the interface area of the cation permeation layer and the anion permeation layer to serve as a water dissociation catalyst.
Dissolving tetrabutylammonium iodide into acetonitrile to obtain organic electrolyte with the concentration of 4mol/L, and adding a metal phthalocyanine compound into the organic electrolyte to reach the concentration of 0.03mol/L to obtain organic composite electrolyte;
dissolving and absorbing carbon dioxide by using an organic composite electrolyte in a gas absorption tower, continuously injecting the organic composite electrolyte containing a large amount of carbon dioxide into the bottom of a cathode chamber, flowing the organic composite electrolyte containing lower concentration carbon dioxide at the upper part of the cathode chamber out of the upper part of the cathode chamber, reintroducing the organic composite electrolyte containing lower concentration carbon dioxide into the gas absorption tower for dissolving and absorbing carbon dioxide, and injecting the obtained organic composite electrolyte containing a large amount of carbon dioxide into the bottom of the cathode chamber of the three-compartment electrolytic cell again, thereby forming a catholyte cycle; continuously injecting 25wt% of KCl solution into the anode chamber, flowing water solution containing lower concentration KCl at the upper part of the anode chamber out of the upper part of the anode chamber, and injecting the water solution into the anode chamber again after the KCl and water are supplemented; water is continuously injected into the middle chamber, and the solution flowing out of the middle chamber is evaporated and separated to obtain potassium hydroxide.
Step four, switching on an electrolysis power supply at normal temperature and normal pressure, controlling the cell voltage to be 6.6V, enabling chloride ions to undergo oxidation reaction on an anode to generate chlorine, enabling potassium ions in an anode chamber to pass through a cation exchange membrane and enter an intermediate chamber to meet hydroxide ions generated by hydrolysis of a bipolar membrane to generate potassium hydroxide, enabling carbon dioxide to undergo electroreduction reaction on a cathode to generate carbon monoxide and carbonate, and enabling carbonate to react with hydrogen ions generated by hydrolysis of the bipolar membrane to generate carbon dioxide and water. The experimental result of the electrolysis for 12 hours period shows that the current efficiency of generating carbon monoxide is stabilized at 94 percent, and the current density is stabilized at 45mA/cm 2 The current efficiency of the generated chlorine gas is stabilized at 95%, and the current density is stabilized at 36mA/cm 2 The generated carbon monoxide and chlorine are respectively stored in a gas storage tank.
Example 8
A bipolar membrane electrolysis method for preparing carbon monoxide by electrolyzing carbon dioxide in an organic electrolyte and simultaneously preparing chlorine and metal hydroxide as byproducts comprises the following specific operation steps:
the method comprises the steps of firstly, dividing a bipolar membrane and sulfonated polyethylene cation exchange membrane electrolytic cell into a cathode chamber, an intermediate chamber and an anode chamber, placing an Ag/Zn alloy electrode in the cathode chamber as a cathode, placing a glassy carbon electrode in the anode chamber as an anode, and adding water in the intermediate chamber. The anion permeation layer of the bipolar membrane is a perfluoropolymer anion permeation layer containing quaternary ammonium and secondary amine, the thickness is 180 micrometers, the cation permeation layer is a sulfonated polyether ether ketone cation permeation layer, the thickness is 190 micrometers, and iridium dioxide/titanium dioxide nano particles are introduced into the interface area of the cation permeation layer and the anion permeation layer to serve as a water dissociation catalyst.
Dissolving tetrabutylammonium iodide into propylene carbonate to obtain organic electrolyte with the concentration of 4mol/L, and adding a metal phthalocyanine compound into the organic electrolyte to reach the concentration of 0.04mol/L to obtain an organic composite electrolyte;
dissolving and absorbing carbon dioxide by using an organic composite electrolyte in a gas absorption tower, continuously injecting the organic composite electrolyte containing a large amount of carbon dioxide into the bottom of a cathode chamber, flowing the organic composite electrolyte containing lower concentration carbon dioxide at the upper part of the cathode chamber out of the upper part of the cathode chamber, reintroducing the organic composite electrolyte containing lower concentration carbon dioxide into the gas absorption tower for dissolving and absorbing carbon dioxide, and injecting the obtained organic composite electrolyte containing a large amount of carbon dioxide into the bottom of the cathode chamber of the three-compartment electrolytic cell again, thereby forming a catholyte cycle; continuously injecting 10wt% LiCl solution into the anode chamber, flowing out the aqueous solution containing low concentration LiCl at the upper part of the anode chamber, supplementing LiCl and water, and then injecting into the anode chamber again; water is continuously injected into the middle chamber, and the solution flowing out of the middle chamber is evaporated and separated to obtain lithium hydroxide.
And fourthly, switching on an electrolysis power supply at normal temperature and normal pressure, controlling the cell voltage to be 6.2V, enabling chloride ions to undergo oxidation reaction on an anode to generate chlorine, enabling lithium ions in an anode chamber to pass through a cation exchange membrane and enter an intermediate chamber to meet hydroxide ions generated by hydrolysis of a bipolar membrane to generate lithium hydroxide, enabling carbon dioxide to undergo electroreduction reaction on a cathode to generate carbon monoxide and carbonate, and enabling carbonate to react with hydrogen ions generated by hydrolysis of the bipolar membrane to generate carbon dioxide and water. The experimental result of the 12-hour long-period electrolysis shows that the current efficiency of generating carbon monoxide is stabilized at 92 percent, and the current density is stabilized at 39mA/cm 2 The current efficiency of the generated chlorine is stabilized at 95%, and the current density is stabilized at32.5mA/cm 2 The generated carbon monoxide and chlorine are respectively stored in a gas storage tank.
Example 9
A bipolar membrane electrolysis method for preparing carbon monoxide by electrolyzing carbon dioxide in an organic electrolyte and simultaneously preparing chlorine and metal hydroxide as byproducts comprises the following specific operation steps:
the method comprises the steps of firstly, dividing an electrolytic cell into a cathode chamber, an intermediate chamber and an anode chamber by using a bipolar membrane and a sulfonated polystyrene cation exchange membrane, placing an Au/Zn alloy electrode in the cathode chamber as a cathode, placing a glassy carbon electrode in the anode chamber as an anode, and adding water in the intermediate chamber. The anion permeation layer of the bipolar membrane is a perfluoropolymer anion permeation layer containing quaternary ammonium and secondary amine, the thickness is 200 micrometers, the cation permeation layer is a sulfonated polyethylene cation permeation layer, the thickness is 250 micrometers, and silica/indium trioxide nano particles are introduced into the interface area of the cation permeation layer and the anion permeation layer to serve as a water dissociation catalyst.
Dissolving tetrabutylammonium bromide into acetonitrile to obtain an organic electrolyte with the concentration of 0.6mol/L, and adding tricarbonyl-2, 2' -bipyridine metal halide into the organic electrolyte to obtain an organic composite electrolyte with the concentration of 0.2 mol/L;
dissolving and absorbing carbon dioxide by using an organic composite electrolyte in a gas absorption tower, continuously injecting the organic composite electrolyte containing a large amount of carbon dioxide into the bottom of a cathode chamber, flowing the organic composite electrolyte containing lower concentration carbon dioxide at the upper part of the cathode chamber out of the upper part of the cathode chamber, reintroducing the organic composite electrolyte containing lower concentration carbon dioxide into the gas absorption tower for dissolving and absorbing carbon dioxide, and injecting the obtained organic composite electrolyte containing a large amount of carbon dioxide into the bottom of the cathode chamber of the three-compartment electrolytic cell again, thereby forming a catholyte cycle; continuously injecting 25wt% NaCl solution into the anode chamber, allowing the water solution containing lower concentration NaCl at the upper part of the anode chamber to flow out from the upper part of the anode chamber, supplementing NaCl and water, and then injecting into the anode chamber again; water is continuously injected into the middle chamber, and the solution flowing out of the middle chamber is evaporated and separated to obtain sodium hydroxide.
And fourthly, switching on an electrolysis power supply at normal temperature and normal pressure, controlling the voltage of a tank to be 6.7V, enabling chloride ions to undergo oxidation reaction on an anode to generate chlorine, enabling sodium ions in an anode chamber to pass through a cation exchange membrane and enter an intermediate chamber to meet hydroxide ions generated by hydrolysis of a bipolar membrane to generate sodium hydroxide, enabling carbon dioxide to undergo electroreduction reaction on a cathode to generate carbon monoxide and carbonate, and enabling carbonate to react with hydrogen ions generated by hydrolysis of the bipolar membrane to generate carbon dioxide and water. The experimental result of the 12-hour long-period electrolysis shows that the current efficiency of generating carbon monoxide is stabilized at 92 percent, and the current density is stabilized at 45mA/cm 2 The current efficiency of the generated chlorine is stabilized at 95%, and the current density is stabilized at 38mA/cm 2 The generated carbon monoxide and chlorine are respectively stored in a gas storage tank.
Example 10
A bipolar membrane electrolysis method for preparing carbon monoxide by electrolyzing carbon dioxide in an organic electrolyte and simultaneously preparing chlorine and metal hydroxide as byproducts comprises the following specific operation steps:
step one, dividing an electrolytic cell into a cathode chamber, an intermediate chamber and an anode chamber by using a bipolar membrane and a perfluorinated sulfonic acid type cation exchange membrane, placing an Au electrode as a cathode in the cathode chamber and placing IrO in the anode chamber 2 ·Ta 2 O 5 The coated titanium electrode served as the anode and water was added to the intermediate chamber. The anion permeation layer of the bipolar membrane is an imidazole polyether-ether-ketone anion permeation layer with the thickness of 240 microns, the cation permeation layer is a sulfonated polyvinylidene fluoride cation permeation layer with the thickness of 250 microns, and aluminum hydroxide is introduced into the interface area of the cation permeation layer and the anion permeation layer to serve as a hydrolysis catalyst.
Dissolving tetrabutylammonium iodide into propylene carbonate to obtain an organic electrolyte with the concentration of 0.9mol/L, and adding imidazole ionic liquid into the organic electrolyte to obtain an organic composite electrolyte with the concentration of 0.4 mol/L;
dissolving and absorbing carbon dioxide by using an organic composite electrolyte in a gas absorption tower, continuously injecting the organic composite electrolyte containing a large amount of carbon dioxide into the bottom of a cathode chamber, flowing the organic composite electrolyte containing lower concentration carbon dioxide at the upper part of the cathode chamber out of the upper part of the cathode chamber, reintroducing the organic composite electrolyte containing lower concentration carbon dioxide into the gas absorption tower for dissolving and absorbing carbon dioxide, and injecting the obtained organic composite electrolyte containing a large amount of carbon dioxide into the bottom of the cathode chamber of the three-compartment electrolytic cell again, thereby forming a catholyte cycle; continuously injecting 22wt% NaCl solution into the anode chamber, allowing the water solution containing lower concentration NaCl at the upper part of the anode chamber to flow out from the upper part of the anode chamber, supplementing NaCl and water, and then injecting into the anode chamber again; water is continuously injected into the middle chamber, and the solution flowing out of the middle chamber is evaporated and separated to obtain sodium hydroxide.
And fourthly, switching on an electrolysis power supply at normal temperature and normal pressure, controlling the cell voltage to be 6.6V, enabling chloride ions to undergo oxidation reaction on an anode to generate chlorine, enabling barium ions in an anode chamber to pass through a cation exchange membrane and enter an intermediate chamber to meet hydroxide ions generated by hydrolysis of a bipolar membrane to generate barium hydroxide, enabling carbon dioxide to undergo electroreduction reaction on a cathode to generate carbon monoxide and carbonate, and enabling carbonate to react with hydrogen ions generated by hydrolysis of the bipolar membrane to generate carbon dioxide and water. The experimental result of the electrolysis for 12 hours period shows that the current efficiency of generating carbon monoxide is stabilized at 94 percent, and the current density is stabilized at 45mA/cm 2 The current efficiency of the generated chlorine gas is stabilized at 96%, and the current density is stabilized at 32mA/cm 2 The generated carbon monoxide and chlorine are respectively stored in a gas storage tank.
While the present invention has been described in detail with reference to the drawings, the present invention is not limited to the above embodiments, and various changes can be made without departing from the spirit of the present invention within the knowledge of those skilled in the art.
Claims (8)
1. A bipolar membrane electrolysis method for preparing carbon monoxide by electrolyzing carbon dioxide in an organic electrolyte and simultaneously preparing chlorine and metal hydroxide as byproducts is characterized by comprising the following steps of: dividing the electrolytic cell into a cathode chamber, an intermediate chamber and an anode chamber by using a bipolar membrane and a cation exchange membrane to form a three-compartment electrolytic cell, wherein the electrolyte in the cathode chamber is an organic composite electrolyte dissolved with a large amount of carbon dioxide, the electrolyte in the intermediate chamber is a metal hydroxide aqueous solution, the electrolyte in the anode chamber is a metal chloride aqueous solution, carbon monoxide is generated on a cathode and chlorine is generated on an anode in the electrolytic reaction process, and the content of the metal hydroxide in the intermediate chamber is increased;
A bipolar membrane separates the cathode chamber from the intermediate chamber, and a cation exchange membrane separates the intermediate chamber from the anode chamber;
the chlorine ions in the anode chamber are subjected to oxidation reaction on the anode to generate chlorine; the metal ions in the anode chamber pass through the cation exchange membrane and enter the middle chamber to meet hydroxide ions generated by the hydrolysis and dissociation of the bipolar membrane, so as to generate metal hydroxide; the carbon dioxide is subjected to electroreduction reaction on the cathode to generate carbon monoxide and carbonate, and the carbonate reacts with hydrogen ions generated by the hydrolysis of the bipolar membrane to generate carbon dioxide and water.
2. The bipolar membrane electrolysis method for preparing carbon monoxide and simultaneously producing chlorine and metal hydroxide by electrolyzing carbon dioxide in an organic electrolyte according to claim 1, wherein the method comprises the following steps: the anion permeable layer in the bipolar membrane is one of an imidazole polyether ether ketone anion permeable layer, a styrene/ethylene benzyl chloride copolymer anion permeable layer containing diamine, a quaternized polyethylene anion permeable layer, a quaternized polyvinyl chloride anion permeable layer, a quaternized polyphenyl ether anion permeable layer, a polysulfone anion permeable layer containing bicyclic amine, a quaternized styrene/divinylbenzene copolymer anion permeable layer and a perfluoropolymer anion permeable layer containing quaternary amine and secondary amine, and the thickness of the anion permeable layer is 15-300 micrometers; the cation permeation layer in the bipolar membrane is one of a sulfonated polyethylene cation permeation layer, a sulfonated polystyrene cation permeation layer, a sulfonated polyether-ether-ketone cation permeation layer, a sulfonated polyvinylidene fluoride cation permeation layer and a perfluorinated sulfonic acid type cation permeation layer, the thickness is 15-300 microns, and a water dissociation catalyst is introduced into the interface area of the cation permeation layer and the anion permeation layer, wherein the water dissociation catalyst is one or a mixture of any proportion of a plurality of polyvinyl acid/polyvinyl pyridinium complex, sulfonated polyether-ether-ketone, chromium hydroxide, zirconium oxide, aluminosilicate, chromium trioxide, nickel oxide, aluminum hydroxide, tin oxide, ferric hydroxide, manganese dioxide, iridium dioxide, titanium dioxide, silicon dioxide, indium trioxide, cobalt trioxide, bismuth, tin, ruthenium, rhodium, palladium, osmium, iridium and platinum.
3. The bipolar membrane electrolysis method for preparing carbon monoxide and simultaneously producing chlorine and metal hydroxide by electrolyzing carbon dioxide in an organic electrolyte according to claim 1, wherein the method comprises the following steps: the cation exchange membrane is one of a sulfonated polyethylene cation exchange membrane, a sulfonated polystyrene cation exchange membrane, a sulfonated polyvinylidene fluoride cation exchange membrane, a chlorosulfonated polyethylene cation exchange membrane and a perfluorosulfonic acid cation exchange membrane.
4. The bipolar membrane electrolysis method for preparing carbon monoxide and simultaneously producing chlorine and metal hydroxide by electrolyzing carbon dioxide in an organic electrolyte according to claim 1, wherein the method comprises the following steps: the organic composite electrolyte in the cathode chamber electrolyte comprises three functional components: the organic solvent is one of dimethyl sulfoxide, N-dimethylformamide, propylene carbonate, N-methylpyrrolidone, diethyl carbonate and acetonitrile or a mixed solvent formed by the solvents according to any proportion, the organic supporting electrolyte is one of quaternary ammonium salt and choline chloride or a mixture of the two supporting electrolytes according to any proportion, and the homogeneous electrocatalyst is one of metalloporphyrin compound, metal phthalocyanine compound, tricarbonyl-2, 2' -bipyridine metal halide, imidazole ionic liquid and pyridine ionic liquid or a mixture formed by the homogeneous electrocatalyst according to any proportion.
5. The bipolar membrane electrolysis method for preparing carbon monoxide and simultaneously producing chlorine and metal hydroxide by electrolyzing carbon dioxide in an organic electrolyte according to claim 1, wherein the method comprises the following steps: the three partitionsThe anode of the chamber electrolytic cell is an iridium oxide coating titanium electrode and IrO 2 ·Ta 2 O 5 The anode chamber electrolyte is a metal chloride aqueous solution, and the cathode is any one of a Cu, au, ag, zn electrode or an alloy of the metals.
6. The bipolar membrane electrolysis method for preparing carbon monoxide and simultaneously producing chlorine and metal hydroxide by electrolyzing carbon dioxide in an organic electrolyte according to claim 5, wherein the method comprises the steps of: the metal chloride aqueous solution is one or a mixture aqueous solution consisting of any proportion of sodium chloride, potassium chloride, lithium chloride and barium chloride.
7. The bipolar membrane electrolysis method for preparing carbon monoxide and simultaneously producing chlorine and metal hydroxide by electrolysis of carbon dioxide in an organic electrolyte according to any one of claims 1 to 6, characterized by comprising the following specific operation steps:
dividing an electrolytic cell into a cathode chamber, an intermediate chamber and an anode chamber by using a bipolar membrane and a cation exchange membrane to form a three-compartment electrolytic cell, respectively placing a cathode and an anode in the cathode chamber and the anode chamber, and adding water in the intermediate chamber;
Step two, organic supporting electrolyte is dissolved in an organic solvent to prepare an organic electrolyte with the concentration of 0.1-4.0 mol/L, a homogeneous electrocatalyst is added into the obtained organic electrolyte, so that the concentration of the homogeneous electrocatalyst reaches 0.01-0.4 mol/L, an organic composite electrolyte is obtained, and a metal chloride aqueous solution with the mass percent concentration of 10% -25% is prepared;
dissolving carbon dioxide into an organic composite electrolyte in a gas absorption tower, continuously injecting the organic composite electrolyte containing a large amount of carbon dioxide into the bottom of a cathode chamber, flowing the organic composite electrolyte containing lower concentration carbon dioxide at the upper part of the cathode chamber out of the upper part of the cathode chamber, and sending the organic composite electrolyte containing lower concentration carbon dioxide into the gas absorption tower again for dissolving and absorbing carbon dioxide, wherein the obtained organic composite electrolyte containing a large amount of carbon dioxide is injected into the bottom of the cathode chamber of the three-compartment electrolytic cell again, so that catholyte circulation is formed; continuously injecting metal chloride aqueous solution into the anode chamber, enabling the aqueous solution containing the metal chloride with lower concentration at the upper part of the anode chamber to flow out of the upper part of the anode chamber, supplementing the metal chloride and water, then injecting the solution into the anode chamber, continuously injecting water into the middle chamber, and evaporating and separating the solution flowing out of the middle chamber to obtain metal hydroxide;
Step four, switching on an electrolysis power supply at normal temperature and normal pressure, controlling the voltage of a tank to be 5.2-9.6V, and enabling chloride ions in an anode chamber to undergo oxidation reaction on an anode to generate chlorine; the metal ions in the anode chamber pass through the cation exchange membrane and enter the middle chamber to meet hydroxide ions generated by the hydrolysis and dissociation of the bipolar membrane, so as to generate metal hydroxide; the carbon dioxide is subjected to electroreduction reaction on the cathode to generate carbon monoxide and carbonate, the carbonate reacts with hydrogen ions generated by the hydrolysis of the bipolar membrane to generate carbon dioxide and water, and the generated carbon monoxide and chlorine are respectively stored in the gas storage tank.
8. The bipolar membrane electrolysis method for preparing carbon monoxide and simultaneously producing chlorine and metal hydroxide by electrolyzing carbon dioxide in an organic electrolyte according to claim 7, wherein the method comprises the steps of: the chlorine generated by the anode reaction and the carbon monoxide generated by the cathode reaction can be independently used as chemical raw materials, and can be mixed for producing phosgene, and the solution flowing out of the middle chamber is evaporated and separated to obtain metal hydroxide.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102912374A (en) * | 2012-10-24 | 2013-02-06 | 中国科学院大连化学物理研究所 | An electrochemical reduction CO2 electrolytic cell with a bipolar membrane as a diaphragm and its application |
| CN107099815A (en) * | 2017-04-24 | 2017-08-29 | 太原师范学院 | A kind of application of Bipolar Membrane surface powder state photochemical catalyst in CO2 reduction |
| CN110983357A (en) * | 2019-12-04 | 2020-04-10 | 昆明理工大学 | Three-chamber diaphragm electrolysis method for preparing carbon monoxide by electrolyzing carbon dioxide and simultaneously producing chlorine and bicarbonate as byproducts |
-
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102912374A (en) * | 2012-10-24 | 2013-02-06 | 中国科学院大连化学物理研究所 | An electrochemical reduction CO2 electrolytic cell with a bipolar membrane as a diaphragm and its application |
| CN107099815A (en) * | 2017-04-24 | 2017-08-29 | 太原师范学院 | A kind of application of Bipolar Membrane surface powder state photochemical catalyst in CO2 reduction |
| CN110983357A (en) * | 2019-12-04 | 2020-04-10 | 昆明理工大学 | Three-chamber diaphragm electrolysis method for preparing carbon monoxide by electrolyzing carbon dioxide and simultaneously producing chlorine and bicarbonate as byproducts |
Non-Patent Citations (2)
| Title |
|---|
| Novel bipolar membrane electrolyzer for CO2 reduction to CO in organic electrolyte with Cl2 and NaOH produced as byproducts;Fengxia Shen et al.;Journal of CO2 Utilization;20231014;102595号第1-10页 * |
| Synergistic Electrochemical CO2 Reduction and Water Oxidation with a Bipolar Membrane;David A. Vermaas et al.;ACS Energy Lett.;20161107;第1143-1148页 * |
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