CN116354460A - Electrochemical process and device for generating electricity and producing fuel through sewage treatment in cooperation - Google Patents
Electrochemical process and device for generating electricity and producing fuel through sewage treatment in cooperation Download PDFInfo
- Publication number
- CN116354460A CN116354460A CN202310089165.XA CN202310089165A CN116354460A CN 116354460 A CN116354460 A CN 116354460A CN 202310089165 A CN202310089165 A CN 202310089165A CN 116354460 A CN116354460 A CN 116354460A
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- Prior art keywords
- hydrazine
- ruthenium
- nitrate
- sewage
- copper
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000010865 sewage Substances 0.000 title claims abstract description 79
- 238000000034 method Methods 0.000 title claims abstract description 42
- 230000008569 process Effects 0.000 title claims abstract description 22
- 239000000446 fuel Substances 0.000 title claims abstract description 17
- 230000005611 electricity Effects 0.000 title claims abstract description 14
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims abstract description 154
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 47
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims abstract description 47
- 239000003054 catalyst Substances 0.000 claims abstract description 40
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 32
- 239000001257 hydrogen Substances 0.000 claims abstract description 31
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- 239000007788 liquid Substances 0.000 claims abstract description 26
- RAESLDWEUUSRLO-UHFFFAOYSA-O aminoazanium;nitrate Chemical compound [NH3+]N.[O-][N+]([O-])=O RAESLDWEUUSRLO-UHFFFAOYSA-O 0.000 claims abstract description 25
- 238000004519 manufacturing process Methods 0.000 claims abstract description 17
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 10
- 230000003647 oxidation Effects 0.000 claims abstract description 10
- 230000009467 reduction Effects 0.000 claims abstract description 6
- 239000012528 membrane Substances 0.000 claims description 33
- 239000006260 foam Substances 0.000 claims description 19
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 18
- 229910017052 cobalt Inorganic materials 0.000 claims description 18
- 239000010941 cobalt Substances 0.000 claims description 18
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 18
- 238000001354 calcination Methods 0.000 claims description 14
- 229910052707 ruthenium Inorganic materials 0.000 claims description 14
- VLWBWEUXNYUQKJ-UHFFFAOYSA-N cobalt ruthenium Chemical compound [Co].[Ru] VLWBWEUXNYUQKJ-UHFFFAOYSA-N 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 12
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 10
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 10
- QDNPJNIUNGYXPA-UHFFFAOYSA-N [Co].[Cu].[Ru] Chemical compound [Co].[Cu].[Ru] QDNPJNIUNGYXPA-UHFFFAOYSA-N 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 230000002195 synergetic effect Effects 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 9
- 229910052802 copper Inorganic materials 0.000 claims description 9
- 239000010949 copper Substances 0.000 claims description 9
- 238000011065 in-situ storage Methods 0.000 claims description 9
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- XCEAGAJKBRACAD-UHFFFAOYSA-N [Cu].[Ru] Chemical compound [Cu].[Ru] XCEAGAJKBRACAD-UHFFFAOYSA-N 0.000 claims description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 8
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 claims description 8
- 238000010276 construction Methods 0.000 claims description 8
- 238000011068 loading method Methods 0.000 claims description 8
- 239000010936 titanium Substances 0.000 claims description 8
- 229910052719 titanium Inorganic materials 0.000 claims description 8
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 7
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 6
- 238000005342 ion exchange Methods 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 230000002572 peristaltic effect Effects 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 239000003011 anion exchange membrane Substances 0.000 claims description 5
- 238000005341 cation exchange Methods 0.000 claims description 5
- 230000001590 oxidative effect Effects 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 238000003860 storage Methods 0.000 claims description 5
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 claims description 4
- 239000011521 glass Substances 0.000 claims description 4
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 239000007800 oxidant agent Substances 0.000 claims description 4
- 238000001556 precipitation Methods 0.000 claims description 4
- -1 ruthenium ions Chemical class 0.000 claims description 4
- 229910001220 stainless steel Inorganic materials 0.000 claims description 4
- 239000010935 stainless steel Substances 0.000 claims description 4
- 239000005750 Copper hydroxide Substances 0.000 claims description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 3
- 239000004202 carbamide Substances 0.000 claims description 3
- 229910001956 copper hydroxide Inorganic materials 0.000 claims description 3
- 238000007731 hot pressing Methods 0.000 claims description 3
- AFEBXVJYLNMAJB-UHFFFAOYSA-N hydrazine;nitric acid Chemical compound NN.O[N+]([O-])=O AFEBXVJYLNMAJB-UHFFFAOYSA-N 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 239000004033 plastic Substances 0.000 claims description 3
- 239000002243 precursor Substances 0.000 claims description 3
- 238000010992 reflux Methods 0.000 claims description 3
- 238000005507 spraying Methods 0.000 claims description 3
- 230000009471 action Effects 0.000 claims description 2
- 239000004744 fabric Substances 0.000 claims description 2
- 239000003365 glass fiber Substances 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 2
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 2
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 2
- 238000010248 power generation Methods 0.000 claims 9
- 230000002194 synthesizing effect Effects 0.000 claims 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 abstract description 16
- 229910021529 ammonia Inorganic materials 0.000 abstract description 8
- 239000002699 waste material Substances 0.000 abstract description 4
- 150000002431 hydrogen Chemical class 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 3
- 239000002440 industrial waste Substances 0.000 abstract 1
- 210000004027 cell Anatomy 0.000 description 11
- 238000005516 engineering process Methods 0.000 description 10
- 238000010586 diagram Methods 0.000 description 8
- 238000000746 purification Methods 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 238000006722 reduction reaction Methods 0.000 description 6
- 239000000741 silica gel Substances 0.000 description 6
- 229910002027 silica gel Inorganic materials 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000007789 gas Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 3
- 241000894007 species Species 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 210000000170 cell membrane Anatomy 0.000 description 2
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- 239000003344 environmental pollutant Substances 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- VJPLIHZPOJDHLB-UHFFFAOYSA-N lead titanium Chemical compound [Ti].[Pb] VJPLIHZPOJDHLB-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 230000002269 spontaneous effect Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- FUSNOPLQVRUIIM-UHFFFAOYSA-N 4-amino-2-(4,4-dimethyl-2-oxoimidazolidin-1-yl)-n-[3-(trifluoromethyl)phenyl]pyrimidine-5-carboxamide Chemical compound O=C1NC(C)(C)CN1C(N=C1N)=NC=C1C(=O)NC1=CC=CC(C(F)(F)F)=C1 FUSNOPLQVRUIIM-UHFFFAOYSA-N 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- BIVUUOPIAYRCAP-UHFFFAOYSA-N aminoazanium;chloride Chemical compound Cl.NN BIVUUOPIAYRCAP-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000010170 biological method Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004769 chrono-potentiometry Methods 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000010411 electrocatalyst Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 239000012493 hydrazine sulfate Substances 0.000 description 1
- 229910000377 hydrazine sulfate Inorganic materials 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910001959 inorganic nitrate Inorganic materials 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
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- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
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- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
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- 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
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- 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
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- C25B1/04—Hydrogen or oxygen by electrolysis of water
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- C—CHEMISTRY; METALLURGY
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- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
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- C25B1/01—Products
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- 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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- 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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- C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
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- C25B11/031—Porous electrodes
- C25B11/032—Gas diffusion electrodes
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- C—CHEMISTRY; METALLURGY
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- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
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- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
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- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
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- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
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- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
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- C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
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- C25B9/23—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms comprising ion-exchange membranes in or on which electrode material is embedded
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
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- C02F2001/46133—Electrodes characterised by the material
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- C02F2001/46142—Catalytic coating
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
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- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
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- C02F2001/46152—Electrodes characterised by the shape or form
- C02F2001/46157—Perforated or foraminous electrodes
- C02F2001/46161—Porous electrodes
- C02F2001/46166—Gas diffusion electrodes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
An electrochemical process and apparatus for generating electricity and producing fuel by sewage treatment is characterized by that at least one of ruthenium-cobalt-base and ruthenium-copper-base catalysts is used to electro-catalytically drive hydrazine oxidation, nitrate reduction and hydrogen separation reactions, and a hydrazine-nitrate battery composed of industrial waste hydrazine and nitrate waste liquid is assembled for generating electricity and producing ammonia. Moreover, the generated electric power can additionally drive a hydrazine sewage water electrolysis cell, so that hydrogen production is realized.
Description
Technical Field
The invention relates to the technical field of electrochemical sewage treatment, in particular to an electrochemical process and a reaction device capable of simultaneously treating hydrazine sewage and nitrate sewage and simultaneously generating electricity, ammonia and hydrogen.
Background
In recent years, rapid developments in urban, agricultural and industrial fields have brought about a series of problems such as greenhouse effect, atmospheric pollution and environmental pollution. The direct discharge of industrial and agricultural and urban domestic sewage can severely pollute surface water resources, thereby leading to ecological system unbalance, and the standard of pollutant discharge is becoming stricter. The pollutants in the current industrial and agricultural and urban domestic sewage mainly comprise organic matters, heavy metal ions, sulfur-containing salts, nitrogen-containing salts, phosphorus-containing salts and the like. Because sewage contains a plurality of substances which are toxic and harmful to human bodies, animals and plants, the direct sewage discharge can not only directly harm life bodies on the earth, but also cause immeasurable harm to the ecological environment. Conventional sewage treatment processes include bio-enzyme catalysis, physical multiple evaporation crystallization technology, chemical Fenton reaction, etc., which inevitably involve complicated separation processes, additional energy consumption and chemical reagent use, thereby increasing sewage treatment costs. In addition, the removal efficiency of contaminants in conventional methods is also unsatisfactory. In view of this, there is a need to develop a novel and efficient sewage treatment technology and process.
In recent years, electrochemical sewage treatment methods have received great attention. Compared with the traditional physical, chemical and biological methods for treating sewage, the electrochemical water treatment method has the advantages of high reaction rate, controllable product selectivity, high sewage purification efficiency and the like. However, the electrolytic cell used in the method has the problems of small volume capacity, large ohmic resistance, single waste liquid treatment and the like, so that the method often consumes excessive electric energy, and the electrolytic cell with high-flux flow of liquid and a specific electrode catalyst are required to be designed, so that the technology is not suitable for being used as an independent sewage treatment process in the aspects of economy and technology.
Disclosure of Invention
The invention aims to solve the defects of the prior electrochemical technology in the sewage treatment direction, and provides an electrochemical process and device for generating electricity and producing fuel cooperatively by sewage treatment, which can treat hydrazine and nitrate sewage and produce electricity, ammonia and hydrogen cooperatively at the same time, thereby achieving the purposes of spontaneously purifying two waste liquids and generating electricity and producing fuel simultaneously.
In order to achieve the above purpose, the invention adopts the following technical scheme:
an electrochemical process for generating electricity and producing fuel by sewage treatment in a synergic manner comprises the following steps:
1) Constructing a hydrazine-nitrate battery and a hydrazine electrolytic tank by adopting a clinging type membrane electrode flow reactor;
2) Driving hydrazine oxidation, nitrate reduction and hydrogen precipitation reaction by adopting a ruthenium cobalt copper-based catalyst; the ruthenium cobalt copper-based catalyst is at least one of ruthenium cobalt-based and ruthenium copper-based catalysts;
3) And highly purifying the hydrazine and nitrate sewage by adopting a mixing and stirring mode under the action of a ruthenium cobalt copper-based catalyst, wherein the concentration range of the hydrazine and nitrate sewage is 0.01-2000 mM.
1. The membrane electrode flow reactor assembly in the invention:
the invention relates to a clinging type membrane electrode flow reactor of a bipolar plate, a cathode current collector, a diaphragm, an anode current collector and a bipolar plate. The bipolar plate material of the assembly can be selected from a titanium plate, a stainless steel plate, a graphite plate or an organic glass plate; the bipolar plate is provided with a flow channel, and two ends of the flow channel are provided with a liquid inlet and a liquid outlet; the liquid flow channel can be a full hollow channel or a serpentine channel; the membrane can be selected from a cation exchange membrane, a proton exchange membrane, an anion exchange membrane or a glass fiber membrane; the liquid inlet and the liquid outlet can be made of iron or plastic external screw pagoda connectors or quick connectors; the lead can be titanium, silver or copper wire; silica gel gaskets are added between the bipolar plates. Finally, holes are formed on the peripheries of the two bipolar plates, and proper plastic or stainless steel bolts and nuts are selected to be screwed up so as to fix the membrane electrode flow reactor; the ruthenium cobalt copper-based catalyst is loaded on the cathode current collector and the anode current collector.
2. The selection and synthesis of the catalyst in the invention:
the catalyst used in the present invention to drive the reaction of hydrazine oxidation, nitrate reduction and hydrogen precipitation is oxides, hydroxides, metals, composite materials thereof, etc. mainly of ruthenium cobalt copper metal. They can be grown directly on the current collector in situ or can be coated on the current collector by spraying and hot pressing. The current collector can be selected from carbon paper, carbon felt, carbon cloth, foam nickel, foam cobalt, foam copper, foam iron, foam titanium, nickel mesh, cobalt mesh, copper mesh, iron mesh, titanium mesh and the like.
Taking ruthenium cobalt bimetallic catalyst synthesized in situ on a foam cobalt current collector as an example. Firstly, a rod-shaped cobalt hydroxide structure grows on foam cobalt by adopting a hydrothermal method, so that the specific surface area of the foam cobalt is expanded, then, ruthenium trichloride is adopted as a raw material to carry out cation exchange in a water phase, so that ruthenium species are loaded on the rod-shaped cobalt hydroxide, and finally, the mixture is calcined in the atmosphere of hydrogen and inert gas to form the ruthenium-cobalt bimetallic catalyst. Wherein urea or hexamethylenetetramine is adopted as a precipitator in hydrothermal process, the temperature is 80-160 ℃ and the time is 4-24 hours; the concentration of ruthenium is 0.01-1 mg mL during ion exchange -1 The reaction time is 0.5-12 h, and the reaction temperature is 0-60 ℃; the calcination temperature is 150-600 ℃, the time is 1-6 h, and the calcination atmosphere is the mixture of hydrogen and inert gas; the synthesized catalyst is in a rod shape, wherein the cobalt loading amount is 1-5 mg cm -2 Ruthenium loading of 0.01-1 mg cm -2 。
In addition, rod-shaped cobalt hydroxide powder can be directly synthesized by adopting a hydrothermal method, then the cobalt hydroxide powder and a certain amount of ruthenium trichloride are subjected to cation exchange in a water phase, so that ruthenium species are loaded on the rod-shaped cobalt hydroxide, then the cobalt hydroxide powder is calcined in the atmosphere of a mixed gas of hydrogen and inert gas to form ruthenium-cobalt bimetallic powder, finally the powder is mixed with a binder and dissolved in an organic solvent, and the mixture is uniformly dispersed and then loaded on a carbon paper current collector in a spraying hot-pressing mode.
The ruthenium-copper-based catalyst is prepared as follows: firstly, preparing a copper hydroxide precursor by adopting electrochemical anodic oxidation or a strong oxidant wet method, and then adopting ruthenium ions to carry out ion exchangeFinally calcining in a reducing atmosphere, wherein the electrochemical anodic oxidation current density is 0.01-100 mA cm -2 The method comprises the steps of carrying out a first treatment on the surface of the The wet reaction adopts an alkalized persulfate solution as a strong oxidant, the reaction pH is 12-15, the ammonium persulfate concentration is 0.01-1M, the reaction temperature is 0-60 ℃, and the reaction time is 1-180 min; the concentration of the ion exchange ruthenium is 0.01-1 mg mL -1 The reaction time is 0.5-12 h, and the reaction temperature is 0-60 ℃; the calcination temperature is 150-500 ℃ and the time is 1-6 h, and the calcination atmosphere is the mixture of hydrogen and inert gas; the synthesized catalyst is in a rod shape, wherein the copper loading capacity is 1-5 mg cm -2 Ruthenium loading of 0.01-1 mg cm -2 。
3. The construction method of the hydrazine-nitrate battery comprises the following steps:
in the invention, the hydrazine and nitrate sewage enters the membrane electrode flow reactor in a liquid circulation flow mode, so that the purposes of sewage purification and electricity generation are realized. Firstly, adopting peristaltic pumps to respectively pour hydrazine and nitrate sewage into anode and cathode flow channels of a membrane electrode flow reactor, then discharging the hydrazine and nitrate sewage and respectively refluxing the hydrazine and nitrate sewage to a hydrazine and nitrate sewage pool, thereby achieving the purpose of circulating flow. Then, the cathode and anode of the membrane electrode flow reactor are connected to an electrochemical workstation, and a certain output voltage or current is set to start the hydrazine-nitrate battery. Through long-time flowing circulation test, hydrazine in the sewage is oxidized into nitrogen and nitrate is reduced into ammonia water, so that the aim of purification is fulfilled. In addition, the electricity extracted from the electrochemical workstation may further drive a hydrazine-contaminated water electrolyzer for hydrogen production. In the reaction process of the hydrazine-nitrate battery, nitrogen generated by oxidization of hydrazine is directly discharged into the atmosphere, ammonia water generated by reduction of nitrate can be separated through a gas stripping technology, so that high-purity and high-concentration ammonia fuel is obtained, and hydrogen generated by a hydrazine electrolysis tank can be directly stored into a gas storage tank through a gas-liquid separator.
4. The construction method of the hydrazine electrolytic cell comprises the following steps:
the construction method of the hydrazine electrolytic cell in the invention is similar to that of a hydrazine-nitrate battery. Firstly, adopting peristaltic pumps to respectively pour hydrazine sewage and potassium hydroxide solution into anode and cathode flow channels of a membrane electrode flow reactor, and then respectively reflux discharged liquid of the anode and cathode flow channels to a hydrazine sewage tank and a potassium hydroxide liquid storage tank, thereby achieving the purpose of circulating flow. Then connecting an electrochemical workstation, inputting the electric power generated by the hydrazine-nitrate battery into the anode and cathode of a hydrazine electrolytic tank, and oxidizing hydrazine in sewage into nitrogen after long-time flowing circulation test so as to achieve the aim of purification; the water in the potassium hydroxide solution is reduced into hydrogen, and the generated hydrogen can be collected by a drainage method or directly stored in a gas storage tank by adopting a gas-liquid separator. If the output power of the hydrazine-nitrate battery and the input power of the hydrazine electrolysis tank are not required to be controlled, the two devices can be directly connected through the lead, and an electrochemical workstation is not required to be additionally adopted as an intermediate medium for energy storage and release.
5. The invention relates to a method for highly purifying hydrazine and nitrate sewage, which comprises the following steps:
in the invention, if electric power collection is not needed or high purification of low-concentration residual hydrazine and nitrate sewage is needed, the two sewage are only needed to be directly mixed in a container tank, then a catalyst is added and stirring is applied.
Compared with the prior art, the technical scheme of the invention has the beneficial effects that:
1. the invention utilizes the characteristic that electrochemical hydrazine oxidation reaction and nitrate reduction reaction can be spontaneously coupled to form a primary cell to treat hydrazine and nitrate sewage, has simple method and environmental protection, does not need to consume extra electric energy, and provides a new idea for the electrochemical technology in the sewage treatment field. The membrane electrode flow reactor designed by the invention is specially used for collecting generated electric energy and ammonia products, and the generated electric energy can also drive a hydrazine sewage water electrolysis tank to produce hydrogen. Therefore, the method of the invention not only can treat the sewage containing hydrazine and nitrate, but also can additionally produce electricity, ammonia and hydrogen, has multiple purposes and high economic benefit.
2. The membrane electrode flow reactor device has compact design, small occupied area, low ohmic resistance and quick gas/liquid transmission, and can start reaction only by respectively pouring sewage into the cathode and anode flow channels of the device. The device not only can assemble the hydrazine-nitrate battery, but also can assemble the hydrazine electrolytic tank, so the applicability is wider.
3. The invention adopts ruthenium-cobalt bimetallic catalyst grown on a foam cobalt substrate in situ as an electrocatalyst for driving hydrazine oxidation, nitrate reduction and hydrogen precipitation reactions, and a hydrazine-nitrate battery assembled by the catalyst has a discharge current density of 100mA cm -2 At the time, the peak power density of 12mW cm -2 The ammonia production rate is 0.37mmol h -1 cm -2 The method comprises the steps of carrying out a first treatment on the surface of the While the hydrazine electrolytic tank can reach 50mA cm only by 0.23V tank pressure -2 Current density, hydrogen production rate of 0.93mmol h -1 cm -2 The method comprises the steps of carrying out a first treatment on the surface of the And the former can spontaneously drive the latter to produce hydrogen with the hydrogen production rate reaching 0.35mmol h -1 cm -2 。
4. According to the invention, the high purification of the hydrazine and nitrate sewage can be realized by only mixing the hydrazine and nitrate sewage with low concentration residues, adding the catalyst and stirring. The concentration of hydrazine and nitrate in the sewage after the reaction is reduced to below 1ppm, the removal efficiency is respectively up to 99.98% and 99.94%, and the repeated effect is excellent. In addition, the technology has the advantages of simple process, convenient equipment construction and easy maintenance, can realize large-scale purification of hydrazine and nitrate sewage, and has industrial application prospect.
Drawings
FIG. 1 is an assembled schematic view of a membrane electrode flow reactor.
FIG. 2 is a scanning electron microscope and elemental distribution diagram of ruthenium cobalt bimetallic catalyst.
Fig. 3 is a schematic and performance diagram of a hydrazine-nitrate battery device.
FIG. 4 is a schematic diagram and performance diagram of a hydrazine electrolyzer.
Fig. 5 is a schematic diagram of a self-driven hydrazine-nitrate cell hydrogen-generating device.
FIG. 6 is a schematic diagram of a hydrazine and nitrate highly purified device and a residual sewage concentration diagram.
Detailed Description
In order to make the technical problems, technical schemes and beneficial effects to be solved more clear and obvious, the invention is further described in detail below with reference to the accompanying drawings and embodiments.
The main components of the hydrazine sewage in the invention are hydrazine hydrate, hydrazine sulfate, hydrazine hydrochloride, other hydrazine-containing derivatives and the like, wherein the concentration range of the hydrazine is 0.01-2000 mM. The main component of the nitrate sewage is inorganic nitrate, wherein the concentration range of the nitrate is 0.01-2000 mM. Some other inorganic salt impurities, such as potassium hydroxide, potassium sulfate, sodium chloride, etc., and some common organic matters, such as fat, alkane, cellulose, protein, etc., are also present in the sewage.
1. The specific assembly mode of the membrane electrode flow reactor in the invention is as follows:
firstly, a hydrazine-nitrate battery membrane electrode flow reactor is built, two flow channels (1X 1 cm) 2 ) And a liquid inlet/outlet (5X 5 cm) 2 ) As a bipolar plate; proton exchange membrane (1.5X1.5 cm) 2 ) As a separator; two blocks grown in situ in cobalt foam (1X 1 cm) 2 ) The ruthenium-cobalt bimetallic catalyst is directly used as a current collector and consumable materials such as a silica gel gasket, a conductive titanium foil, a bolt, a nut and the like with hollowed-out middle. As shown in FIG. 1, firstly, an organic glass plate with a serpentine flow channel and four nuts are used as a substrate (step 1), then a layer of middle hollow silica gel gasket is covered (step 2), a current collector and a lead titanium foil are put in (step 3), then a layer of proton exchange membrane is covered in the middle (step 4), then a layer of middle hollow silica gel gasket is covered (step 5), then the current collector and the lead titanium foil are put in the middle (step 6), finally another organic glass plate is covered (step 7), and the sealing is performed by screwing bolts (step 8).
The proton exchange membrane adopted in the assembly process can not only prevent the cathode current collector from being in direct contact with the anode current collector and avoid short circuit, but also effectively inhibit the serial flow of the nitrate sewage and the ammonia water product cathode and anode cavity, thereby facilitating the subsequent separation and collection of ammonia water.
The assembly process of the hydrazine electrolysis cell membrane electrode flow reactor is the same as that of the hydrazine-nitrate cell membrane electrode flow reactor, and only the proton exchange membrane is changed into the anion exchange membrane.
2. The ruthenium cobalt bimetallic catalyst is synthesized by the following steps:
in the invention, a ruthenium cobalt bimetallic catalyst grown on a foam cobalt current collector in situ is taken as an example. The specific synthesis scheme is as follows: firstly, preparing a solution of cobalt chloride with the concentration of 0.05M and urea with the concentration of 0.25M, and uniformly stirring. Then 30mL of the solution is put into a lining of a polytetrafluoroethylene reaction kettle, and a piece of 2X 4cm is put into the lining 2 Is covered with a cover and sealed in a stainless steel container. The mixture was placed in a forced air oven, the hydrothermal reaction temperature was set to 90℃and the duration was 10 hours. And after the hydrothermal reaction is finished and cooled, taking out the foamed cobalt substrate, and washing the foamed cobalt substrate to successfully grow the rod-shaped cobalt hydroxide on the foamed cobalt substrate in situ. Next, the foamed cobalt is immersed vertically in 60mL of RuCl 3 Solution (0.05 mg mL) -1 ) The solution was stirred at room temperature until a precipitate formed in the solution, the cobalt foam was removed, rinsed clean, and dried. Finally placing the mixture in a tube furnace to calcine at 250 ℃ for 3 hours under the calcination atmosphere of 5% H 2 Ar mixture. After the reaction is finished, the ruthenium-cobalt bimetallic catalyst which grows on the foam cobalt substrate in situ can be obtained, and a scanning electron microscope image and an element distribution diagram of the ruthenium-cobalt bimetallic catalyst are shown as figure 2.
Besides the ruthenium cobalt catalyst, the ruthenium copper catalyst also has the same effect, and the ruthenium copper bimetallic catalyst can be directly synthesized in situ on the foam copper current collector. The specific scheme is as follows: placing foamy copper into an alkalified ammonium persulfate solution to form a rod-shaped copper hydroxide structure, thereby expanding the specific surface area of the foamy copper, then adopting ruthenium trichloride as a raw material to carry out cation exchange in a water phase, enabling ruthenium species to be loaded on the rod-shaped copper hydroxide, and finally calcining the mixture of hydrogen and inert gas in the atmosphere to form the ruthenium-copper bimetallic catalyst.
3. Construction of a hydrazine-nitrate battery device in the invention:
in the invention, hydrazine and nitrate sewage enters the membrane electrode flow reactor in a liquid circulation flow mode. The specific mode is as follows: as shown in FIG. 3a, the peristaltic pump and the silica gel tube are adopted to communicate the anode flow passage of the hydrazine-nitrate battery membrane electrode flow reactor and the hydrazine sewage pool, and the cathode flow passage and the nitrate sewage pool are communicated in the same way, the concentration of the hydrazine and the nitrate sewage is 0.1M, and the flow rate is the same as thatControlling at 150mL min -1 . And then connecting the cathode and anode titanium wires of the battery with an electrochemical workstation for testing, wherein a chronopotentiometric method is adopted in the testing mode, so that a polarization curve and a power density curve are drawn. As shown in FIG. 3b, when the output current density is 100mA cm -2 When the battery is in use, the maximum power of the battery can reach 12mW cm -2 Is a peak power density of (c). As shown in FIG. 3c, the chronopotentiometry shows that the cell can be operated continuously and stably for 20 hours, during which the slow decrease in output voltage is attributable to the rapid consumption of hydrazine and nitrate in the wastewater, so that the cell performance can be recovered by supplementing only hydrazine and nitrate, during which the average ammonia yield is 0.37mmol h -1 cm -2 . The produced ammonia water can be combined with the stripping technology, so that the ammonia water solution with high purity and high concentration can be produced.
4. Construction of a hydrazine-nitrate battery device in the invention:
in the invention, hydrazine sewage and potassium hydroxide solution enter a membrane electrode flow reactor in a liquid circulation flow mode. The specific mode is as follows: as shown in FIG. 4a, a peristaltic pump and a silica gel tube are adopted to communicate an anode flow passage of a membrane electrode flow reactor of a hydrazine electrolysis tank with a hydrazine sewage pool, and a cathode flow passage of the hydrazine electrolysis tank is communicated with a potassium hydroxide liquid storage tank in the same way, wherein the concentration of hydrazine sewage is 0.1M, the concentration of potassium hydroxide solution is 1M, and the flow rate is controlled to be 150mL min -1 . And then connecting the cathode and anode titanium wires of the electrolytic tank with an electrochemical workstation for testing, wherein a chronopotentiometric method is adopted in the testing mode, so that a polarization curve is drawn. As shown in FIGS. 4b and 4c, the cell can reach 50mA cm with a cell pressure of only 0.23V -2 Current density and stable operation for at least 20h, hydrogen production rate of 0.93mmol h -1 cm -2 。
5. The method for driving the hydrazine-nitrate battery to produce hydrogen by the hydrazine electrolysis cell device comprises the following steps:
as shown in FIG. 5, in the invention, two hydrazine-nitrate batteries are connected in series only through a lead, then the anode of the hydrazine-nitrate battery is connected with the cathode of an anion exchange membrane hydrazine electrolytic tank, and the cathode of the hydrazine-nitrate battery is connected with the anode of the anion exchange membrane hydrazine electrolytic tank, so that spontaneous hydrogen production can be realized, and the hydrogen production rate is 0.35mmol cm -1 h -1 。
6. The invention relates to a method for highly purifying hydrazine and nitrate sewage, which comprises the following steps:
as shown in FIG. 6a, the invention can realize the high purification of the hydrazine and nitrate sewage by only mixing the residual/low-concentration hydrazine and nitrate waste liquid in the same container tank and then putting a catalyst. As shown in FIG. 6b, by adjusting the concentration ratio of hydrazine to nitrate sewage, one of the concentrations can be reduced to below 1 ppm. For example, when the concentrations of hydrazine and nitrate to be charged are 40 and 10mM, respectively, and the treatment time of one day has elapsed, only 0.26 and 0.36ppm of hydrazine and nitrate remain in the solution after the reaction, respectively, with removal efficiencies as high as 99.98% and 99.94%. In addition, the content of nitrite as a by-product in the solution after completion of the reaction was only 0.07ppm. Finally, it is notable that the catalyst can be reused at least 8 times, the hydrazine and (nitrite) residues always being below 1.1ppm, the removal efficiency still remaining above 99%, as shown in fig. 6 c.
The principle of the invention is as follows:
standard electrode potential for hydrazine oxidation is-1.16 vs. Standard Hydrogen Electrode (SHE), anodic reaction equation: n (N) 2 H 4 -4e - +4OH - →N 2 +4H 2 O; whereas the standard electrode potential for the nitrate reduction reaction is-0.12 v vs. NO (NO) 3 - +8e - +7H 2 O→NH 3 ·H 2 O+9OH - . Therefore, the two cathodes and the anodes are in reactive coupling to form a spontaneous hydrazine-nitrate primary battery, and the discharge voltage of the battery can reach 1.04V at most. The nitrogen generated by the anode in the battery can be directly discharged into the atmosphere, and the ammonia water generated by the cathode can be recycled as a product with high economic value through a stripping technology. Because the system can additionally generate electricity, the hydrazine-nitrate battery assembled by the system can spontaneously drive a hydrazine sewage water electrolysis tank, nitrogen generated by an anode of the hydrazine-nitrate battery is directly discharged into the atmosphere, and hydrogen with high economic value generated by a cathode of the hydrazine-nitrate battery can be directly collected and reused.
Claims (10)
1. An electrochemical process for generating electricity and producing fuel by sewage treatment is characterized by comprising the following steps:
1) Constructing a hydrazine-nitrate battery and a hydrazine electrolytic tank by adopting a clinging type membrane electrode flow reactor;
2) Driving hydrazine oxidation, nitrate reduction and hydrogen precipitation reaction by adopting a ruthenium cobalt copper-based catalyst; the ruthenium cobalt copper-based catalyst is at least one of ruthenium cobalt-based and ruthenium copper-based catalysts.
2. An electrochemical process for the synergistic power generation and fuel production by sewage treatment as claimed in claim 1, wherein: the method also comprises the step of highly purifying the hydrazine and nitrate sewage by adopting a mixing and stirring mode under the action of the ruthenium cobalt copper-based catalyst, wherein the concentration range of the hydrazine and nitrate sewage is 0.01-2000 mM.
3. An electrochemical process for the synergistic power generation and fuel production by sewage treatment as claimed in claim 1, wherein the construction of the hydrazine-nitrate cell comprises: the hydrazine and nitrate sewage water respectively flow into the anode flow channel and the cathode flow channel of the membrane electrode flow reactor through peristaltic pumps, and then are discharged and respectively flow back to the hydrazine and nitrate sewage water tanks, so that the circulating flow is realized.
4. An electrochemical process for the synergistic power generation and fuel production by sewage treatment as claimed in claim 1, wherein the construction of the hydrazine electrolysis cell comprises: and adopting peristaltic pumps to respectively pour hydrazine sewage and potassium hydroxide solution into anode and cathode flow channels of the membrane electrode flow reactor, and then respectively reflux discharged liquid of the anode and cathode flow channels to a hydrazine sewage tank and a potassium hydroxide liquid storage tank, thereby realizing circulating flow.
5. An electrochemical process for the synergistic power generation and fuel production by sewage treatment as claimed in claim 1, wherein: the electric power generated by the hydrazine-nitrate battery is input into the anode and cathode of the hydrazine electrolytic tank, the hydrazine in the sewage is oxidized into nitrogen, the nitrate is reduced into ammonia water, and the water in the potassium hydroxide solution is reduced into hydrogen through flow circulation.
6. An electrochemical process for the synergistic power generation and fuel production by sewage treatment as claimed in claim 1, wherein: the membrane electrode flow reactor comprises a bipolar plate, a cathode current collector, a diaphragm, an anode current collector and a bipolar plate which are sequentially arranged; the bipolar plate is provided with a flow channel, and two ends of the flow channel are provided with a liquid inlet and a liquid outlet; the ruthenium cobalt copper-based catalyst is loaded on the cathode current collector and the anode current collector.
7. An electrochemical process for the synergistic power generation and fuel production by sewage treatment as claimed in claim 6, wherein: the bipolar plate is selected from a titanium plate, a stainless steel plate, a graphite plate or an organic glass plate; the flow channel is a serpentine channel or a full hollow channel; the liquid inlet and the liquid outlet are selected from an external thread pagoda joint or a quick-connect joint made of iron or plastic materials; the membrane is a proton exchange membrane, an anion exchange membrane, a cation exchange membrane or a glass fiber membrane.
8. An electrochemical process for the synergistic power generation and fuel production by sewage treatment as claimed in claim 6, wherein: the ruthenium cobalt copper-based catalyst directly grows on the current collector in situ, or is covered on the current collector in a spraying hot-pressing mode; the current collector is selected from carbon paper, carbon felt, carbon cloth, foam nickel, foam cobalt, foam copper, foam iron, foam titanium, nickel net, cobalt net, copper net, iron net or titanium net.
9. An electrochemical process for the synergistic power generation and fuel production by sewage treatment as claimed in claim 1, wherein the ruthenium copper based catalyst is prepared as follows: firstly, synthesizing a cobalt hydroxide precursor by a hydrothermal method, then carrying out ion exchange by ruthenium ions, and finally calcining in a reducing atmosphere, wherein urea or hexamethylenetetramine is adopted as a precipitant in the hydrothermal process, and the temperature is 80-160 ℃ and the time is 4-24 hours; the concentration of ruthenium is 0.01-1 mg mL during ion exchange -1 The reaction time is 0.5-12 h, and the reaction temperature is 0-60 ℃; the calcination temperature is 150-600 ℃ and the calcination time is 1-6 h, and the calcination atmosphere is the mixture of hydrogen and inert gasThe method comprises the steps of carrying out a first treatment on the surface of the The synthesized catalyst is in a rod shape, wherein the cobalt loading amount is 1-5 mg cm -2 Ruthenium loading of 0.01-1 mg cm -2 。
10. An electrochemical process for the synergistic power generation and fuel production by sewage treatment as claimed in claim 1, wherein the ruthenium copper based catalyst is prepared as follows: firstly preparing a copper hydroxide precursor by adopting electrochemical anodic oxidation or a strong oxidant wet method, then adopting ruthenium ions to carry out ion exchange, and finally calcining in a reducing atmosphere, wherein the electrochemical anodic oxidation current density is 0.01-100 mA cm -2 The method comprises the steps of carrying out a first treatment on the surface of the The wet reaction adopts an alkalized persulfate solution as a strong oxidant, the reaction pH is 12-15, the ammonium persulfate concentration is 0.01-1M, the reaction temperature is 0-60 ℃, and the reaction time is 1-180 min; the concentration of the ion exchange ruthenium is 0.01-1 mg mL -1 The reaction time is 0.5-12 h, and the reaction temperature is 0-60 ℃; the calcination temperature is 150-500 ℃ and the time is 1-6 h, and the calcination atmosphere is the mixture of hydrogen and inert gas; the synthesized catalyst is in a rod shape, wherein the copper loading capacity is 1-5 mg cm -2 Ruthenium loading of 0.01-1 mg cm -2 。
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