WO1996034997A1 - Element electrochimique et procede de separation d'une solution de sulfate et de production d'une solution d'hydroxyde, de l'acide sulfurique et un halogene gazeux - Google Patents
Element electrochimique et procede de separation d'une solution de sulfate et de production d'une solution d'hydroxyde, de l'acide sulfurique et un halogene gazeux Download PDFInfo
- Publication number
- WO1996034997A1 WO1996034997A1 PCT/US1995/016123 US9516123W WO9634997A1 WO 1996034997 A1 WO1996034997 A1 WO 1996034997A1 US 9516123 W US9516123 W US 9516123W WO 9634997 A1 WO9634997 A1 WO 9634997A1
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- WO
- WIPO (PCT)
- Prior art keywords
- solution
- ions
- sulfate
- membrane
- cell
- Prior art date
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- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 title claims abstract description 59
- 238000000034 method Methods 0.000 title claims abstract description 58
- 230000008569 process Effects 0.000 title claims abstract description 55
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 229910052736 halogen Inorganic materials 0.000 title claims abstract description 35
- 150000002367 halogens Chemical class 0.000 title claims abstract description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 title claims abstract description 33
- 239000012528 membrane Substances 0.000 claims abstract description 84
- 229910000039 hydrogen halide Inorganic materials 0.000 claims abstract description 42
- 239000012433 hydrogen halide Substances 0.000 claims abstract description 42
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000007789 gas Substances 0.000 claims abstract description 32
- -1 halogen halide Chemical class 0.000 claims abstract description 31
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims abstract description 29
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000000460 chlorine Substances 0.000 claims abstract description 19
- 239000001257 hydrogen Substances 0.000 claims abstract description 18
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 18
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 17
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052938 sodium sulfate Inorganic materials 0.000 claims abstract description 14
- 235000011152 sodium sulphate Nutrition 0.000 claims abstract description 14
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 9
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 8
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 8
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 5
- 239000011734 sodium Substances 0.000 claims abstract description 5
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims abstract description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 4
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims abstract description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 4
- 229910052936 alkali metal sulfate Inorganic materials 0.000 claims abstract description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 4
- 239000011737 fluorine Substances 0.000 claims abstract description 4
- 229910000042 hydrogen bromide Inorganic materials 0.000 claims abstract description 4
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims abstract description 4
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910000043 hydrogen iodide Inorganic materials 0.000 claims abstract description 4
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000011630 iodine Substances 0.000 claims abstract description 3
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 66
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 48
- 150000002500 ions Chemical class 0.000 claims description 41
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 33
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 17
- 230000001590 oxidative effect Effects 0.000 claims description 17
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 13
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 7
- 229910001413 alkali metal ion Inorganic materials 0.000 claims description 5
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 claims description 5
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 5
- 229910001415 sodium ion Inorganic materials 0.000 claims description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 239000011575 calcium Substances 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 239000011777 magnesium Substances 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 claims description 2
- WNSFXAVCFLWMHB-UHFFFAOYSA-N azane sulfuric acid hydrate Chemical compound N.N.N.O.OS(O)(=O)=O WNSFXAVCFLWMHB-UHFFFAOYSA-N 0.000 claims 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052921 ammonium sulfate Inorganic materials 0.000 abstract description 3
- 235000011130 ammonium sulphate Nutrition 0.000 abstract description 3
- 230000000712 assembly Effects 0.000 abstract description 3
- 238000000429 assembly Methods 0.000 abstract description 3
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 abstract 1
- 229910052939 potassium sulfate Inorganic materials 0.000 abstract 1
- 235000011151 potassium sulphates Nutrition 0.000 abstract 1
- 210000004027 cell Anatomy 0.000 description 73
- 238000006243 chemical reaction Methods 0.000 description 22
- 239000000463 material Substances 0.000 description 22
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 20
- 229920000557 Nafion® Polymers 0.000 description 16
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 11
- 238000004519 manufacturing process Methods 0.000 description 11
- 239000001301 oxygen Substances 0.000 description 11
- 229910052760 oxygen Inorganic materials 0.000 description 11
- 239000003054 catalyst Substances 0.000 description 9
- 239000011262 electrochemically active material Substances 0.000 description 9
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical compound FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 9
- 239000004809 Teflon Substances 0.000 description 8
- 229920006362 Teflon® Polymers 0.000 description 8
- 238000000909 electrodialysis Methods 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 238000012545 processing Methods 0.000 description 7
- 239000006227 byproduct Substances 0.000 description 6
- 239000000376 reactant Substances 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 239000003011 anion exchange membrane Substances 0.000 description 5
- 230000008901 benefit Effects 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 238000005341 cation exchange Methods 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 5
- 230000007797 corrosion Effects 0.000 description 5
- 238000011068 loading method Methods 0.000 description 5
- 239000005518 polymer electrolyte Substances 0.000 description 5
- 125000000542 sulfonic acid group Chemical group 0.000 description 5
- 229910000873 Beta-alumina solid electrolyte Inorganic materials 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 238000007086 side reaction Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000004888 barrier function Effects 0.000 description 3
- 238000001311 chemical methods and process Methods 0.000 description 3
- 238000010960 commercial process Methods 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- OBTWBSRJZRCYQV-UHFFFAOYSA-N sulfuryl difluoride Chemical compound FS(F)(=O)=O OBTWBSRJZRCYQV-UHFFFAOYSA-N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 210000003850 cellular structure Anatomy 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 229920002313 fluoropolymer Polymers 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- XMHIUKTWLZUKEX-UHFFFAOYSA-N hexacosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCC(O)=O XMHIUKTWLZUKEX-UHFFFAOYSA-N 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000000976 ink Substances 0.000 description 2
- 229920000554 ionomer Polymers 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 229910052712 strontium Inorganic materials 0.000 description 2
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- RPAJSBKBKSSMLJ-DFWYDOINSA-N (2s)-2-aminopentanedioic acid;hydrochloride Chemical class Cl.OC(=O)[C@@H](N)CCC(O)=O RPAJSBKBKSSMLJ-DFWYDOINSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229920006169 Perfluoroelastomer Polymers 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
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- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000004035 construction material Substances 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical class Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 239000004811 fluoropolymer Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910000856 hastalloy Inorganic materials 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000003295 industrial effluent Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 238000012552 review Methods 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
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 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
- C25B1/24—Halogens or compounds thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/42—Electrodialysis; Electro-osmosis ; Electro-ultrafiltration; Membrane capacitive deionization
- B01D61/44—Ion-selective electrodialysis
-
- 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
- C25B1/14—Alkali metal compounds
- C25B1/16—Hydroxides
-
- 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
- C25B1/22—Inorganic acids
-
- 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
- C25B1/24—Halogens or compounds thereof
- C25B1/26—Chlorine; Compounds thereof
-
- 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
- C25B15/00—Operating or servicing cells
- C25B15/08—Supplying or removing reactants or electrolytes; Regeneration of electrolytes
-
- 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
- C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
- C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
- C25B9/19—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms
- 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
-
- 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
- C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
- C25B9/60—Constructional parts of cells
- C25B9/65—Means for supplying current; Electrode connections; Electric inter-cell connections
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/0204—Non-porous and characterised by the material
- H01M8/0206—Metals or alloys
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/0204—Non-porous and characterised by the material
- H01M8/0213—Gas-impermeable carbon-containing materials
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/24—Grouping of fuel cells, e.g. stacking of fuel cells
- H01M8/2465—Details of groupings of fuel cells
- H01M8/247—Arrangements for tightening a stack, for accommodation of a stack in a tank or for assembling different tanks
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
- H01M2300/0082—Organic polymers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/0204—Non-porous and characterised by the material
- H01M8/0206—Metals or alloys
- H01M8/0208—Alloys
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/0204—Non-porous and characterised by the material
- H01M8/0223—Composites
- H01M8/0228—Composites in the form of layered or coated products
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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
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Definitions
- the present invention relates to an electro ⁇ chemical cell and a process for splitting a solution and producing a hydroxide, sulfuric acid and a halogen gas.
- the cell and the process may convert either an anhydrous or an aqueous hydrogen halide, such as hydrogen chloride, to a halogen gas, such as chlorine gas, and a. solution such as a sodium sulfate aqueous solution, to form sulfuric acid and sodium hydroxide, along with its co-product, hydrogen.
- Hydrogen chloride (HC1) or hydrochloric acid is a reaction by-product of many manufacturing processes which use chlorine.
- chlorine is used to manufacture polyvinyl chloride, isocyanates, and chlorinated hydrocarbons/fluorinated hydrocarbons, with hydrogen chloride as a by-product of these processes.
- supply so exceeds demand hydrogen chloride or the acid produced often cannot be sold or used, even after careful purification. Shipment over long distances is not economically feasible. Discharge of the acid or chloride ions into waste water streams is environmentally unsound. Recovery and feedback of the chlorine to the manufacturing process is the most desirable route for handling the HC1 by-product.
- a number of commercial processes have been developed to convert HC1 into usable chlorine gas. See, e.g., F. R. Minz, "HCl-Electrolysis - Technology for Recycling Chlorine", Bayer AG, Conference on Electrochemical Processing, Innovation & Progress, Glasgow, Scotland, UK, 4/21-4/23, .1993.
- the current electrochemical commercial process is known as the Uhde process.
- aqueous HCl solution of approximately 22% is fed at 65° to 80° C to both compartments of an electrochemical cell, where exposure to a direct current in the cell results in an electro ⁇ chemical reaction and a decrease in HCl concentration to 17% with the production of chlorine gas and hydrogen gas.
- a polymeric separator divides the two compartments.
- the process requires recycling of dilute (17%) HCl solution produced during the electrolysis step and regenerating an HCl solution of 22% for feed to the electrochemical cell.
- the overall reaction of the Uhde process is expressed by the equation:
- the chlorine gas produced by the Cttide process is wet, usually containing about 1% to 2% water. This wet chlorine gas must then be further processed to produce a dry, usable gas. If the concentration of HCl in the water becomes too low, it is possible for oxygen to be generated from the water present in the Uhde process. This possible side reaction of the Uhde process due to the presence of water, is expressed by the equation:
- the presence of water in the Uhde system limits the current densities at which the cells can perform to less than 500 amps./ft. 2 , because of this side reaction.
- the side reaction results in reduced electrical efficiency and corrosion of the cell components.
- Balko employs an electrolytic cell having a solid polymer electrolyte membrane. Hydrogen chloride, in the form of hydrogen ions and chloride ions in aqueous solution, is introduced into an electrolytic cell. The solid polymer electrolyte membrane is bonded to the anode to permit transport from the anode surface into the membrane. In Balko, controlling and minimizing the oxygen evolution side reaction is an important consideration. Evolution of oxygen decreases cell efficiency and leads to rapid corrosion of components of the cell. The design and configuration of the anode pore size and electrode thickness employed by Balko maximizes transport of the chloride ions.
- Electrodialysis a technology based on the use of cation-exchange and/or anion exchange membranes and of an electric field to effect ion separations, has been the subject of many recent books, articles and papers. See, for example, "Membrane Handbook", edited by .S.W. Ho and K.K. Sirkar, Van Nostrand Reinhold, New York; "The Green Potential of Electrochemistry, Part 2 Application” by D. Pletcher and N.L. Weinberg, Chemical Engineering. November, 1992, pg. 132 - 141. In recent years, DeNora Permelec, spA, of Milan, Italy, has developed the HYDRINA ® process, which generates sodium hydroxide without producing chlorine, using principles of electrodialysis.
- Fig. 1 herein shows a schematic of a three-component cell, shown generally at 1, for splitting sodium sulfate.into sulfuric acid and sodium hydroxide.
- cell 1 includes an anode 2, an anion-exchange membrane membrane 4, a cation exchange membrane 6 and a cathode 8.
- An aqueous solution of sodium sulfate is introduced into a central compartment bounded by anion exchange membrane 4, facing anode 2.
- anion exchange membrane 4 facing anode 2.
- sulfate ions migrate toward the anode and pass through the anion exchange membrane, where they combine with protons produced from water.
- the water is introduced into the anode compartment, where, by means of an electrochemical reaction, it is converted into protons and oxygen.
- Sodium ions from the sodium sulfate migrate through cation-exchange membrane 6 to the cathode compartment, which is also fed with water or dilute sodium hydroxide, whereby they combine with hydroxyl ions formed by the electro ⁇ chemical reaction of the reduction of water to hydrogen and hydroxyl ion.
- the products of the electrodialysis are sulfuric acid and sodium hydroxide, and the gases, oxygen and hydrogen.
- ion-selective membranes that is, membranes which permit only cations (cation exchange membranes) or anions (anion exchange membranes) to pass therethrough, and reject ions of opposite charge.
- a number of such membranes are now commercially available, such as a membrane which is made of hydrated, copolymers of polytetrafluoroethylene and poly-sulfonyl fluoride vinyl ether-containing pendant sulfonic acid groups, and sold under the trademark "NAFION” (hereinafter referred to as NAFION ® ) by E. I. du Pont de Nemours and Company of Wilmington, Delaware (hereinafter referred to as "DuPont”) .
- the present invention solves the problems of the prior art by providing a single process and apparatus for recycling a hydrogen halide and sulfate solution into useful products. More specifically, the present invention solves the problems of the prior art by providing a process and an electrochemical cell which permit simultaneous production of three useful materials, fundamental to the modern chemical industry, halogen gas, such as chlorine, an acid, such as sulfuric acid, and a base, such as sodium hydroxide, from two materials, very often formed as a by-product of chemical processes, and under environmental restraint and facing large excesses in the market place, such as hydrogen chloride and sodium sulfate.
- halogen gas such as chlorine
- an acid such as sulfuric acid
- a base such as sodium hydroxide
- Such process and cell are especially useful at a plant site where both hydrogen chloride and sodium sulfate are produced, and where the products of such a process and cell could be recycled to other production processes.
- the electrochemical cell and the process of the present invention use an essentially anhydrous hydrogen halide as a reactant.
- This process allows for direct processing of anhydrous hydrogen halide which is a by-product of manufacturing processes, without first dissolving the hydrogen halide in water.
- This direct production of essentially dry halogen gas when done, for example, for chlorine gas, is less capital intensive than processes of the prior art, which require separation of water from the chlorine gas.
- This direct production of essentially dry halogen gas also requires lower investment costs than the electrochemical conversions of hydrogen chloride of the prior art. This advantage can translate directly into lower power costs per pound of say, chlorine, generated than in the aqueous electro ⁇ chemical processes of the prior art.
- the direct production of essentially dry halogen gas also provides a process which produces drier chlorine gas with fewer processing steps as compared to that produced by electrochemical or catalytic systems of the prior art, thereby simplifying processing conditions and reducing capital costs.
- a process for producing a solution of hydroxide, sulfuric acid and a halogen gas from a hydrogen halide and a sulfate solution wherein hydrogen halide is fed to a first compartment of an electrochemical cell and is transported to an anode of the cell; a sulfate solution is fed to a second compartment of the cell, wherein the sulfate solution comprises s ⁇ ulfate ions and another ion; the hydrogen halide is oxidized at the anode to produce halogen gas and protons, and the protons are transported through a first cation-transporting membrane; the first membrane rejects the sulfate, ions and the sulfate ions join the protons to form a sulfuric acid solution; water is fed to a third compartment of the cell and is reduced to hydrogen and hydroxyl ion; and a second membrane
- an electrochemical cell for producing a hydroxide solution, sulfuric acid and a halogen gas from a hydrogen halide and a sulfate solution, comprising means for introducing a sulfate solution, wherein the sulfate solution comprises sulfate ions and another type of ion; means for introducing hydrogen halide to a second compartment; means for oxidizing the hydrogen halide to produce halogen gas and protons; first cation-transporting means for transporting the protons therethrough, wherein the first cation- transporting means is disposed in contact with the oxidizing means and the first cation-transporting means rejects the sulfate ions and the sulfate ions join the protons to form a sulfuric acid solution; means for introducing water to a third compartment; means for reducing the water to hydrogen and hydroxyl ion; and second cation-transporting means for transporting the other ions therethrough, wherein
- Fig. 1 is a schematic view of a three-compartment electrodialysis cell of the prior art for splitting sodium sulfate into sulfuric acid and sodium hydroxide.
- Fig. 2 is an exploded, cross-sectional view of an electrochemical cell which produces an alkali metal hydroxide, sulfuric acid and a halogen by splitting an alkali metal solution according to the present invention.
- Fig. 3A is a is a top cross-sectional view of the anode mass flow field as shown in Fig. 2.
- Fig. 3B is a is a top cross-sectional view of the cathode mass flow field as shown in Fig. 2.
- an electrochemical cell for producing a hydroxide solution, sulfuric acid and a halogen gas from a hydrogen halide and a solution.
- a cell is shown generally at 10 in Fig. 2.
- hydrogen as well as chlorine gas, is produced.
- the cell of the present invention may use anhydrous hydrogen chloride as a reactant and directly produce essentially dry chlorine gas, which will be referred to as the anhydrous case.
- directly means that the electrochemical cell obviates the need to remove water from the halogen gas produced or the need to convert essentially anhydrous hydrogen halide to aqueous hydrogen halide before electrochemical treatment.
- the cell of the present invention may also use aqueous hydrogen chloride as a reactant and produce wet chlorine, which will be referred to as the aqueous case.
- the cell of the present invention will be described as using hydrogen chloride as a reactant to produce chlorine gas, in either the anhydrous or the aqueous case.
- this cell may alternatively be used to produce other halogen gases, such as bromine, fluorine (in the anhydrous case only) and iodine from a respective anhydrous hydrogen halide, such as hydrogen bromide, hydrogen fluoride and hydrogen iodide.
- the cell is described and shown for splitting a sodium sulfate solution,
- the electrochemical cell of the present invention comprises means for introducing a sulfate solution to a first compartment.
- the inlet means preferably comprises an inlet 22 as shown in Fig. 2.
- a sulfate solution which is sodium sulfate NaS0 4 (aq) in Fig. 2, is introduced through inlet 22.
- the sulfate solution comprises sulfate ions and another type of ion.
- the other type of ion may be either an alkali metal ion, an alkaline earth metal ion or an ammonium ion.
- the present invention need not be limited to these ions, provided that the ions are capable of being transmitted through a cation-transporting membrane.
- the hydroxide solution is an alkali metal solution
- the sulfate solution is an alkali metal sulfate solution.
- the alkali metal is either sodium or potassium.
- the hydroxide solution is an alkaline earth metal hydroxide solution
- the sulfate solution is an alkaline earth metal sulfate solution.
- Examples of the alkaline earth metals particularly useful with the present invention include calcium and magnesium.
- the other type of ion is an ammonium ion
- the hydroxide solution is an ammonium solution
- the sulfate solution is an ammonium sulfate solution.
- the electrochemical cell of the present invention also comprises means for introducing hydrogen halide to a second compartment.
- the means for introducing hydrogen halide is an inlet 14 as shown in Fig. 2.
- electrochemical cell 10 has an anode-side outlet 16 as shown in Fig. 2. Since in the preferred embodiment, anhydrous HCl is carried through the inlet, and chlorine gas is carried through the outlet, the inlet and the outlet may be lined with a fluoropolymer, sold under the trademark TEFLON ® PFA by DuPont.
- the electrochemical cell of the present invention also comprises means for oxidizing hydrogen halide to produce halogen gas and protons.
- the oxidizing means comprises means for oxidizing molecules of essentially anhydrous hydrogen halide, preferably anhydrous hydrogen chloride, to produce essentially dry halogen gas, preferably, chlorine gas.
- the oxidizing means comprises means for oxidizing ions of aqueous hydrogen halide, preferably hydrogen chloride, to produce wet halogen gas, preferably chlorine gas.
- the oxidizing means comprises an anode 12 as shown in Fig.
- membrane 18 may be a proton- conducting membrane.
- Membrane 18 may be a commercial cationic membrane made of a fluoro- or perfluoro- polymer, preferably a copolymer of two or more fluoro or perfluoromonomers, at least one of which has pendant sulfonic acid groups. The presence of carboxylic groups is not desirable, because those groups tend to decrease the conductivity of the membrane when they are protonated.
- Suitable resin materials are available commercially or can be made according to patent literature. They include fluorinated polymers with side chains of the type -CF 2 CFRS0 3 H and
- Suitable cationic membranes which are made of hydrated, ' copolymers of polytetrafluoroethylene and poly-sulfonyl fluoride vinyl ether-containing pendant sulfonic acid groups, are offered by DuPont under the trademark "NAFION” (hereinafter referred to as NAFION ® ) .
- NAFION ® membranes containing pendant sulfonic acid groups include NAFION ® 117,
- NAFION ® 324 and NAFION ® 417 are both supported and has an equivalent weight of 1100 g., equivalent weight being defined as the amount of resin required to neutralize one liter of a 1M sodium hydroxide solution. w
- the other two types of NAFION ® are both supported on a fluorocarbon fabric, the equivalent weight of NAFION ® 417 also being 1100 g.
- NAFION ® 324 has a two-layer structure, a 125 ⁇ -thick membrane having an equivalent weight of 1100 g., and a 25 ⁇ m-thick membrane having an equivalent weight of 1500 g.
- the sulfate solution comprises sulfate ions and another type of ion.
- the sulfate ions join the protons which are transported through membrane 18 to form a sulfuric acid solution, H 2 S0 4 a mecanic ) as shown in Fig. 2.
- the electrochemical cell of the present invention also comprises means for introducing water to a third compartment.
- the means for introducing water comprises an inlet 24. Water, H 2 0 as shown in Fig. 2, enters the cell through inlet 24.
- the electrochemical cell of the present invention also comprises means for reducing the water to produce hydroxyl ions and hydrogen.
- the reducing means comprises a cathode 20.
- the cathode reduces the water to hydrogen and hydroxyl ion.
- the hydrogen (H 2 ) leaves the cell through an outlet 26 as shown in Fig. 2.
- the electrochemically active material may comprise any type of catalytic or metallic material or metallic oxide, as long as the material can support charge transfer.
- the electro- chemically active material may comprise a catalyst material such as platinum, ruthenium, osmium, rhenium, rhodium, iridium, palladium, gold, titanium or zirconium and the oxides, alloys or mixtures thereof.
- the oxides of these materials are not used for the cathode.
- Other catalyst materials suitable for use with the present invention may include, but are not limited to, transition metal macro cycles in monomeric and polymeric forms and transition metal oxides, including perovskites and pyrochores.
- the electrochemically active material may comprise a catalyst material on a support material.
- the support material may comprise particles of carbon and particles of polytetrafluoro ⁇ ethylene, which is sold under the trademark "TEFLON” (hereinafter referred to as TEFLON ® ) , commercially available from DuPont.
- the electrochemically active material may be bonded by virtue of the TEFLON ® to a support structure of carbon paper or graphite cloth and hot-pressed to the cation-transporting membrane.
- the hydrophobic nature of TEFLON ® does not allow a film of water to form at the anode. A water barrier in the electrode would hamper the diffusion of HCl to the reaction sites.
- the electrodes are preferably hot- pressed into the membrane in order to have good contact between the catalyst and the membrane.
- the loadings of electrochemically active material may vary based on the method of application to the membrane.
- Hot-pressed, gas-diffusion electrodes typically have loadings of 0.10 to 0.50 mg/cm 2 .
- Lower loadings are possible with other available methods of deposition, such as distributing them as thin films from inks onto the membranes, as described in Wilson and Gottesfeld, "High Performance Catalyzed Membranes of Ultra-low Pt Loadings for Polymer Electrolyte Fuel Cells", Los Alamos National Laboratory, J. Electrochem. Soc, Vol. 139, No.
- the electrochemical cell of the present invention also comprises second cation-transporting means for transporting the other type of ion therethrough, wherein the second cation-transporting means is disposed in contact with the reducing means.
- the second cation-transporting means preferably comprises a second cation-transporting membrane 19 as shown in Fig. 2. As shown in Fig.
- first cation-transporting membrane 18 and second cation-transporting membrane 19 face each other.
- the second cation-transporting membrane may be made of any of the materials or constructed like any of the configurations as described above for the first cation-transporting membrane.
- each membrane 20/membrane 19 are similar to membrane electrode assemblies (MEA's) of the prior art, except that in the present invention, each membrane is disposed in contact with only one electrode, rather than two. Both the first and the second membranes are hydrated by the water present in the feed of the aqueous sodium sulfate.
- the second cation-transporting means, or membrane rejects the hydroxyl ions, as illustrated by the angled arrow off membrane 19, and the hydroxyl ions are joined with the other type of ions to form a solution of hydroxide, such as sodium hydroxide NaOH(aq) as shown in Fig. 2, which exits the cell through outlet 26.
- the electrochemical cell of the first and second embodiments further comprises an anode flow field 28 disposed in contact with the anode and a cathode flow field 30 disposed in contact with the cathode.
- the flow fields are electrically conductive, and act as both mass and current flow fields.
- the purpose of the anode flow field is to get reactants, such as anhydrous HCl in the first and second embodiments, to the anode and products, such as essentially dry chlorine gas from the anode.
- the purpose of the cathode flow field is to get reactants, such as liquid water to the cathode and products, such as hydrogen gas, from the cathode.
- anode mass flow field 28 includes a plurality of flow channels 29 as shown in Fig.
- Fig. 3A for directing the anhydrous or aqueous HCl to the anode and chlorine gas away from the anode
- the cathode mass flow field 30 includes a plurality of flow channels 31 as shown in Fig. 3B for directing the water added through cathode-side inlet 24 in Fig. 2 to the cathode and sodium hydroxide and hydrogen away from the cathode.
- Fig. 3A is a cut-away, top cross-sectional view of the anode mass flow field of Fig. 1
- Fig. 3B is a cut-away top cross-sectional view of the cathode mass flow field of Fig. 1.
- the flow fields and the flow channels may have a variety -of configurations and may. be made of different materials. Also, the flow fields may be made in any manner known to one skilled in the art.
- the electrochemical cell of the present invention may also comprise an anode mass flow manifold 32 and a cathode mass flow field manifold 34 as shown in Fig. 2.
- the purpose of such manifolds is to form a frame around the anode mass flow field and the anode, and the cathode mass flow field and the cathode, respectively.
- These manifolds are preferably made of a corrosion resistant material, such as TEFLON ® PFA.
- a gasket 36, 38 also contributes to forming a frame around the respective anode and cathode mass flow fields.
- These gaskets are preferably also made of a corrosion resistant material, such as polytetrafluoroethylene, sold under the trademark TEFLON ® PTFE by DuPont.
- the electrochemical cell of the first and second embodiments also comprises an anode current bus 46 and a cathode current bus 48 as shown in Fig. 2.
- the current buses conduct current to and from a voltage source (not shown) .
- anode current bus 46 is connected to the positive terminal of a voltage source
- cathode current bus 48 is connected to the negative terminal of the voltage source, so that when voltage is supplied to the cell, current flows through all of the cell components to the right of current bus 46 as shown in Fig. 2, including current bus 48, from which it returns to the voltage source.
- the current buses are made of a conductor material, such as copper.
- the electrochemical cell of the present invention further comprises a current distributor disposed on one side of the flow field.
- An anode current distributor 40 is shown in Fig. 2 disposed on one side of anode flow field 28, and a cathode current distributor 42 is shown in Fig. 2 disposed on one side of cathode flow field 30.
- the anode current distributor collects current from the anode bus and distributes it to the anode by electronic conduction.
- the cathode current distributor collects current from the cathode and distributes it to the cathode bus by electronic conduction.
- the anode and the cathode current distributors preferably each comprise a non-porous layer.
- the anode current distributor thus provides a barrier between the anode current bus and the hydrogen halide, such as hydrogen chloride and the halogen gas, such as chlorine.
- the cathode current distributor provides a barrier between the cathode current bus and the liquid water added to the cathode inlet and hydrogen gas (H 2 (g) ) and the sodium hydroxide solution, NaOH(aq) exiting outlet 24.
- the current distributors of the present invention may be made of a variety of materials, and the material used for the anode current distributor need not be the same as the material used for the cathode current distributor.
- the anode current distributor is made of platinized tantalum
- the cathode current distributor is made of a nickel-base alloy, such as UNS10665, sold as HASTELLOY ® B-2, by Haynes, International.
- the electrochemical cell also comprises a conductive structural support 44 disposed in contact with anode current distributor 40.
- the support on the anode side is preferably made of UNS31603 (316L stainless steel) .
- a seal 45 preferably in the form of an O-ring made from a perfluoroelastomer, sold under the trademark KALREZ ® by DuPont, is disposed between structural support 44 on the anode side and anode current distributor 40.
- anode current bus 46 in Fig. 2
- structural support 44 is shown in front of anode current bus 46 in Fig. 2, it is within the scope of the present invention for the structural support to be placed behind the anode current bus (i.e., to the left of bus 46 as shown in Fig. 2) and still achieve the same results.
- the cathode current distributor acts as a corrosion-resistant structural backer on the cathode side. This piece can be drilled and tapped to accept the TEFLON ® PFA fitting, which is used for the inlet and outlet.
- the sulfate solution comprises sulfate ions and another type of ion.
- the other type of ion may be either an alkali metal ion, an alkaline earth metal ion or an ammonium ion.
- the present invention need not be limited to these ions, provided that the ions are capable of passing through the cation-exchange membrane.
- the hydroxide solution is an alkali metal solution
- the sulfate solution is an alkali metal sulfate solution.
- the alkali metal is either sodium or potassium.
- the hydroxide solution is an alkaline earth metal solution
- the sulfate solution is an alkaline earth metal sulfate solution.
- alkaline earth metals suitable for use with the process of the present invention are magnesium and calcium.
- the other type of ion is an ammonium ion
- the hydroxide solution is an ammonium solution
- the sulfate solution is an ammonium sulfate solution.
- hydrogen halide is fed to a first compartment of an electrochemical cell, such as cell 10, through an inlet, such as inlet 14 as shown in Fig. 2.
- the hydrogen halide is transported to an anode, such as anode 12 as shown in Fig. 2.
- anode current distributor 40 collects current fromthe anode bus and distributes it to the anode by electronic conduction.
- the hydrogen halide is transported to an anode, such as anode 12 as shown in Fig. 2.
- molecules of essentially anhydrous hydrogen halide are transported to the anode.
- the hydrogen halide is oxidized at the anode to produce halogen gas, which is shown as Cl and which exits the cell through anode-side outlet 16 and protons, shown as H + as shown in Fig. 2.
- ions of aqueous hydrogen halide are fed to the first compartment through inlet 14 and are oxidized at the anode.
- the equation for the anode reaction in the aqueous case is: Electrical . Energy 2H+ + 2C1 ⁇ »-Cl 2 + 2H + + 2e ⁇
- a sulfate solution which comprises sulfate ions and another type of ions, is fed through an inlet, such as inlet 22, to a second compartment of the cell.
- the second compartment is disposed between a first cation- transporting membrane, such as membrane 18, and a second cation-transporting membrane 19, and the second cation-transporting membrane is disposed in contact with a cathode, such as cathode 20 as shown in Fig. 2.
- the protons produced by the oxidation of hydrogen halide at the anode are transported through the first cation-transporting membrane, which is disposed in contact with anode 12 as shown in Fig. 2.
- the first membrane rejects the sulfate ions, shown as S0 4 TM in Fig.
- the second membrane rejects the hydroxyl ions as illustrated by the OH" and the angled arrow extending off membrane 19.
- the hydroxyl ions are joined with the other type of ions, which in the illustrated case are sodium ions, to form a solution of alkali metal hydroxide, shown as NaOH(aq) in Fig. 2.
- Cathode current distributor 42 collects current from cathode 20 and distributes it to cathode bus 48.
- the electrochemical cell of the present invention can be operated over a wide range of temperatures.
- Room temperature operation is an advantage, due to the ease of use of the cell.
- operation at elevated temperatures provides the advantages of improved kinetics and increased electrolyte conductivity. Higher temperatures result in lower cell voltages.
- limits on temperature occur because of the properties of the materials used for elements of the cell.
- the properties of a NAFION ® membrane change when the cell is operated above 120° C.
- the properties of a polymer electrolyte membrane make it difficult to operate a cell at temperatures above 150 C. With a membrane made of other materials, such as a ceramic material like beta-alumina, it is possible to operate a cell at temperatures above 200° C.
- electrochemical cell of present invention at atmospheric pressure.
- the cell could be run at differential pressure gradients, which change the transport characteristics of water or other components in the cell, including the membrane.
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Abstract
L'invention porte sur un élément électrochimique et un procédé d'utilisation d'un halogénure d'hydrogène pour la scission d'une solution de sulfate et de production d'une solution d'hydroxyde, d'acide sulfurique et un halogène gazeux. La solution de sulfate peut en particulier consister en une solution de sulfate de métal alcalin (sodium ou potassium), en une solution de métal alcalino-terreux, ou en une solution de sulfate d'ammonium. L'élément et le procédé peuvent recourir à un halogénure d'hydrogène anhydre ou aqueux par exemple du chlorure ou du fluorure d'hydrogène dans l'option anhydre, ou du bromure ou de l'iodure d'hydrogène ou à un halogène gazeux sec tel que le chlore, le fluor, le brome ou l'iode pour produire des ions hydrogène servant à scinder la solution de métal alcalin pour donner de l'acide sulfurique. L'élément comporte deux systèmes de membranes dans lesquels une anode (12) est en contact avec une membrane (18) et une cathode (20), en contact avec une autre membrane (19), la solution de sulfate étant introduite entre les ensembles membrane-électrode.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
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AU44213/96A AU4421396A (en) | 1995-05-01 | 1995-12-13 | Electrochemical cell and process for splitting a sulfate sol ution and producing a hydroxide solution, sulfuric acid and a halogen gas |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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US43160595A | 1995-05-01 | 1995-05-01 | |
US08/431,605 | 1995-05-01 |
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WO1996034997A1 true WO1996034997A1 (fr) | 1996-11-07 |
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PCT/US1995/016123 WO1996034997A1 (fr) | 1995-05-01 | 1995-12-13 | Element electrochimique et procede de separation d'une solution de sulfate et de production d'une solution d'hydroxyde, de l'acide sulfurique et un halogene gazeux |
Country Status (2)
Country | Link |
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AU (1) | AU4421396A (fr) |
WO (1) | WO1996034997A1 (fr) |
Cited By (21)
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US7749476B2 (en) | 2007-12-28 | 2010-07-06 | Calera Corporation | Production of carbonate-containing compositions from material comprising metal silicates |
US7754169B2 (en) | 2007-12-28 | 2010-07-13 | Calera Corporation | Methods and systems for utilizing waste sources of metal oxides |
US7753618B2 (en) | 2007-06-28 | 2010-07-13 | Calera Corporation | Rocks and aggregate, and methods of making and using the same |
US7771684B2 (en) | 2008-09-30 | 2010-08-10 | Calera Corporation | CO2-sequestering formed building materials |
US7790012B2 (en) | 2008-12-23 | 2010-09-07 | Calera Corporation | Low energy electrochemical hydroxide system and method |
US7815880B2 (en) | 2008-09-30 | 2010-10-19 | Calera Corporation | Reduced-carbon footprint concrete compositions |
US7829053B2 (en) | 2008-10-31 | 2010-11-09 | Calera Corporation | Non-cementitious compositions comprising CO2 sequestering additives |
US7875163B2 (en) | 2008-07-16 | 2011-01-25 | Calera Corporation | Low energy 4-cell electrochemical system with carbon dioxide gas |
US7887694B2 (en) | 2007-12-28 | 2011-02-15 | Calera Corporation | Methods of sequestering CO2 |
US7931809B2 (en) | 2007-06-28 | 2011-04-26 | Calera Corporation | Desalination methods and systems that include carbonate compound precipitation |
US7939336B2 (en) | 2008-09-30 | 2011-05-10 | Calera Corporation | Compositions and methods using substances containing carbon |
US7966250B2 (en) | 2008-09-11 | 2011-06-21 | Calera Corporation | CO2 commodity trading system and method |
US7993500B2 (en) | 2008-07-16 | 2011-08-09 | Calera Corporation | Gas diffusion anode and CO2 cathode electrolyte system |
US7993511B2 (en) | 2009-07-15 | 2011-08-09 | Calera Corporation | Electrochemical production of an alkaline solution using CO2 |
US8137444B2 (en) | 2009-03-10 | 2012-03-20 | Calera Corporation | Systems and methods for processing CO2 |
US8357270B2 (en) | 2008-07-16 | 2013-01-22 | Calera Corporation | CO2 utilization in electrochemical systems |
US8491858B2 (en) | 2009-03-02 | 2013-07-23 | Calera Corporation | Gas stream multi-pollutants control systems and methods |
US8834688B2 (en) | 2009-02-10 | 2014-09-16 | Calera Corporation | Low-voltage alkaline production using hydrogen and electrocatalytic electrodes |
US8869477B2 (en) | 2008-09-30 | 2014-10-28 | Calera Corporation | Formed building materials |
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GB2073251A (en) * | 1980-04-02 | 1981-10-14 | Gen Electric | Anode for reducing oxygen generation in the electrolysis of hydrogen chloride |
US4561945A (en) * | 1984-07-30 | 1985-12-31 | United Technologies Corporation | Electrolysis of alkali metal salts with hydrogen depolarized anodes |
-
1995
- 1995-12-13 WO PCT/US1995/016123 patent/WO1996034997A1/fr active Application Filing
- 1995-12-13 AU AU44213/96A patent/AU4421396A/en not_active Abandoned
Patent Citations (2)
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GB2073251A (en) * | 1980-04-02 | 1981-10-14 | Gen Electric | Anode for reducing oxygen generation in the electrolysis of hydrogen chloride |
US4561945A (en) * | 1984-07-30 | 1985-12-31 | United Technologies Corporation | Electrolysis of alkali metal salts with hydrogen depolarized anodes |
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