EP0356802B1 - Elektrochemisches Verfahren zur Herstellung von Chromsäure - Google Patents
Elektrochemisches Verfahren zur Herstellung von Chromsäure Download PDFInfo
- Publication number
- EP0356802B1 EP0356802B1 EP89115030A EP89115030A EP0356802B1 EP 0356802 B1 EP0356802 B1 EP 0356802B1 EP 89115030 A EP89115030 A EP 89115030A EP 89115030 A EP89115030 A EP 89115030A EP 0356802 B1 EP0356802 B1 EP 0356802B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- solution
- chromic acid
- electrolysis
- sodium
- dichromate
- 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.)
- Expired - Lifetime
Links
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 title claims description 94
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 title claims description 89
- 238000000034 method Methods 0.000 title claims description 49
- 230000008569 process Effects 0.000 title claims description 39
- 238000004519 manufacturing process Methods 0.000 title claims description 15
- 238000005868 electrolysis reaction Methods 0.000 claims description 66
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 34
- 239000012528 membrane Substances 0.000 claims description 33
- 150000001768 cations Chemical class 0.000 claims description 30
- 239000012452 mother liquor Substances 0.000 claims description 24
- 238000005406 washing Methods 0.000 claims description 22
- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical compound [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 claims description 19
- 239000012535 impurity Substances 0.000 claims description 16
- 229910001415 sodium ion Inorganic materials 0.000 claims description 15
- 238000001704 evaporation Methods 0.000 claims description 12
- 230000008020 evaporation Effects 0.000 claims description 12
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 11
- 238000002425 crystallisation Methods 0.000 claims description 11
- 230000008025 crystallization Effects 0.000 claims description 10
- 238000002386 leaching Methods 0.000 claims description 10
- 230000029087 digestion Effects 0.000 claims description 9
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 7
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 150000004679 hydroxides Chemical class 0.000 claims description 5
- 229910052720 vanadium Inorganic materials 0.000 claims description 4
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 claims 1
- 238000010952 in-situ formation Methods 0.000 claims 1
- 239000000243 solution Substances 0.000 description 146
- JHWIEAWILPSRMU-UHFFFAOYSA-N 2-methyl-3-pyrimidin-4-ylpropanoic acid Chemical compound OC(=O)C(C)CC1=CC=NC=N1 JHWIEAWILPSRMU-UHFFFAOYSA-N 0.000 description 69
- PXLIDIMHPNPGMH-UHFFFAOYSA-N sodium chromate Chemical compound [Na+].[Na+].[O-][Cr]([O-])(=O)=O PXLIDIMHPNPGMH-UHFFFAOYSA-N 0.000 description 48
- 210000004379 membrane Anatomy 0.000 description 34
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 33
- 239000007788 liquid Substances 0.000 description 29
- 238000006243 chemical reaction Methods 0.000 description 28
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 26
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 21
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 16
- 239000013078 crystal Substances 0.000 description 15
- 239000001257 hydrogen Substances 0.000 description 14
- 229910052739 hydrogen Inorganic materials 0.000 description 14
- 229910002092 carbon dioxide Inorganic materials 0.000 description 13
- 239000001569 carbon dioxide Substances 0.000 description 12
- 229910052760 oxygen Inorganic materials 0.000 description 12
- 239000001301 oxygen Substances 0.000 description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 11
- -1 hydroxide ions Chemical class 0.000 description 11
- KIEOKOFEPABQKJ-UHFFFAOYSA-N sodium dichromate Chemical compound [Na+].[Na+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KIEOKOFEPABQKJ-UHFFFAOYSA-N 0.000 description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 10
- 239000007789 gas Substances 0.000 description 10
- 229910000029 sodium carbonate Inorganic materials 0.000 description 10
- 239000007787 solid Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 8
- 238000001556 precipitation Methods 0.000 description 8
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 8
- 235000017557 sodium bicarbonate Nutrition 0.000 description 8
- 238000001816 cooling Methods 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 238000010979 pH adjustment Methods 0.000 description 7
- 230000020477 pH reduction Effects 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 6
- 229910052804 chromium Inorganic materials 0.000 description 6
- 239000011651 chromium Substances 0.000 description 6
- 238000005192 partition Methods 0.000 description 6
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 5
- 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 description 5
- 239000002253 acid Substances 0.000 description 5
- 239000003513 alkali Substances 0.000 description 5
- 229910052791 calcium Inorganic materials 0.000 description 5
- 239000011575 calcium Substances 0.000 description 5
- 238000004140 cleaning Methods 0.000 description 5
- 239000012065 filter cake Substances 0.000 description 5
- 239000000725 suspension Substances 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 229920000557 Nafion® Polymers 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 4
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 229920006395 saturated elastomer Polymers 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 3
- PBJULHHTBNLTOR-UHFFFAOYSA-L [Cr](=O)(=O)([O-])O[Cr](=O)(=O)[O-].[Na+].[Cr](=O)(=O)(O)O.[Na+] Chemical compound [Cr](=O)(=O)([O-])O[Cr](=O)(=O)[O-].[Na+].[Cr](=O)(=O)(O)O.[Na+] PBJULHHTBNLTOR-UHFFFAOYSA-L 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 230000005012 migration Effects 0.000 description 3
- 238000013508 migration Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 2
- 239000000292 calcium oxide Substances 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- DNWNZRZGKVWORZ-UHFFFAOYSA-N calcium oxido(dioxo)vanadium Chemical compound [Ca+2].[O-][V](=O)=O.[O-][V](=O)=O DNWNZRZGKVWORZ-UHFFFAOYSA-N 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 2
- 239000004035 construction material Substances 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 229910052741 iridium Inorganic materials 0.000 description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000005507 spraying Methods 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
- 125000001424 substituent group Chemical group 0.000 description 2
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 239000004801 Chlorinated PVC Substances 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 206010053615 Thermal burn Diseases 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- UPHIPHFJVNKLMR-UHFFFAOYSA-N chromium iron Chemical compound [Cr].[Fe] UPHIPHFJVNKLMR-UHFFFAOYSA-N 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 239000011476 clinker brick Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 208000016253 exhaustion Diseases 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 229920002313 fluoropolymer Polymers 0.000 description 1
- 238000001640 fractional crystallisation Methods 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- LIKBJVNGSGBSGK-UHFFFAOYSA-N iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Fe+3].[Fe+3] LIKBJVNGSGBSGK-UHFFFAOYSA-N 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001603 reducing effect Effects 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000029219 regulation of pH Effects 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 230000005070 ripening Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical class [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 210000002023 somite Anatomy 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 229910001936 tantalum oxide Inorganic materials 0.000 description 1
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical compound FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 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
- C25B1/22—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
- C25B15/00—Operating or servicing cells
- C25B15/02—Process control or regulation
-
- 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
- C25B15/085—Removing impurities
Definitions
- Chromic acid CrO3 is technically produced using three different processes:
- the third method membrane electrolysis, avoids this disadvantage and the associated losses of chromium of sodium dichromate in aqueous solution.
- the electrochemical process as described, for example, in Canadian patent specification CA-A-739 447, is based on the principle that is common to membrane electrolysis with a cation-selective membrane, namely the migration of the cations located in an anode chamber through the one that forms the partition to the cathode chamber cation-selective membrane in the cathode chamber under the influence of the electric field.
- Embodiments of the electrochemical process for the production of chromic acid are described in the patent specification CA-A-739 447.
- the sodium ions migrate in an electric field through the membrane into the cathode compartment filled with water or aqueous solution and form the hydroxide ions formed on the cathode under hydrogen evolution, an aqueous solution containing sodium ions, while in the anode chamber the remaining dichromate ions are electrically neutralized by the hydrogen cations formed on the anode with simultaneous oxygen evolution.
- this process amounts to a substitution of the sodium ions in the sodium dichromate with hydrogen ions, that is to say the formation of chromic acid.
- the migration of the sodium ions through the Membrane increasingly accompanied by the migration of the hydrogen ions formed in the anode compartment, so that the use of electrical current for the desired process of sodium removal from the anode part, also called current efficiency, is steadily decreasing.
- the chromic acid must then be separated from these solutions by fractional crystallization.
- a mother liquor remains which contains the sodium dichromate which has not yet been converted electrochemically and residues of chromic acid which have not crystallized out.
- This solution is usefully used again for further conversion into chromic acid in the electrolysis process.
- the following problems result from these process principles: On the one hand, the mother liquor adhering to the chromic acid crystals and consisting of almost concentrated sodium dichromate solution must be carefully washed off in order to obtain a pure product; on the other hand, all impurities which are introduced with the sodium dichromate solution are accumulated in the system and ultimately discharged with and in the chromic acid crystals, since only the electrolysis gases hydrogen and oxygen leave the process and the membrane separating the anode compartment for anions and also for polyvalent cations is largely impermeable.
- DE-A-3 020 261 describes a process for the electrochemical production of chromic acid from dichromate, the aim of which is to operate the production of chromic acid with a high current efficiency and to remove the impurities introduced with the dichromate.
- the process of DE-A-3 020 261 is essentially characterized by the use of a three-room cell, the dichromate solution entering the middle room and exiting from there, poor in dichromate, and sodium ions at the cathode chamber separated by a cation-selective membrane during the flow and Gives off dichromations to the anode space separated by a diaphragm or an anion-selective membrane.
- DE-A-3 020 260 describes the cleaning of sodium chromate solution for the electrochemical production of chromic acid by subjecting the sodium chromate solution to electrolysis in the anode compartment of a two-room cell with a cation-selective partition and the cationic impurities in the membrane precipitate with simultaneous formation of sodium dichromate in the anode compartment and of an alkaline solution containing sodium ions in the cathode compartment, as is known per se from US Pat. No. 3,305,463.
- the sodium chromate / sodium dichromate solution purified in this way is converted electrochemically into chromic acid in the aforementioned manner.
- the object of the present invention is to provide a process with which a very pure, crystalline chromic acid is produced under economic conditions while maintaining the advantages of the electrochemical process for the production of chromic acid.
- the present invention thus relates to a process for the preparation of chromic acid by multi-stage electrolysis of dichromate and / or monochromate solutions in two-room electrolysis cells, their anode and cathode compartments are separated by cation exchange membranes, at temperatures from 50 to 90 ° C., the dichromate and / or monochromate solutions being obtained by digestion of chromium ores and leaching, characterized in that the monochromate solution obtained after leaching, if appropriate after the removal of aluminum, Vanadium and other impurities at 20 to 110 ° C to a pH of 8 to 12 by adding and / or in situ production of carbonate in an amount of 0.01 to 0.18 mol / l (at 300 to 500 g / l Na2CrO4) sets, the precipitated carbonates or hydroxides are separated, the solution is concentrated to a content of 750 to 1000 g / l Na2CrO4, converted under pressure with CO2 into a dichromate-containing solution, which introduces dichromate
- alkali metal dichromates and therefrom the chromic acid technically only chromium iron is used, which is mixed first with sodium carbonate or sodium carbonate / sodium hydroxide solution or sodium hydroxide solution, occasionally with the addition of alkaline earth metal oxides and / or carbonates, in particular calcium oxide and / or calcium carbonate, as an alkaline melting medium and secondly in a mixture with a lean agent consisting essentially of iron (III) oxide or hydroxide, preferably so-called re-ore from the leaching stage described below, is exposed at temperatures above 1000 ° C. to the action of oxygen-containing gases, preferably air.
- the comminuted material is leached out, usually in countercurrent, over several stages in order to obtain sodium chromate as a solution with a Na2CrO4 content of approx. 300 to 500 g / l.
- a pH value of 7.0 to 9.5 is necessary to keep the sodium chromate solution as low as possible. This pH adjustment can take place during leaching or in the solution after separation from the leached solid.
- the required pH adjustment is carried out with dichromate or with chromic acid or with chromic acid / sodium dichromate mixtures or with sodium chromate / sodium dichromate solutions, preferably with those which are used later in the process after acidification Carbon dioxide occur under pressure or with mixtures of said, preferably used sodium chromate / sodium dichromate solutions with sodium dichromate-chromic acid solutions, the latter being removed from the chromic acid electrolysis crystallization cycle for the purpose of discharging impurities.
- the sodium chromate solution freed from the impurities which can be precipitated at pH 7.0 to 9.5, unless the digestion of the chromium ore has been carried out in such a way that vanadium cannot dissolve during leaching, is now in the form of calcium in the form known per se of calcium oxide or calcium hydroxide in aqueous solution or slurry added to precipitate the vanadium as calcium vanadate.
- the calcium is used in a stoichiometric excess, taking into account the calcium dissolved in the leaching of the kiln clinker.
- the remaining sodium chromate solution is brought to 50 to 100.degree. C., preferably 70 to 85.degree. C., to precipitate the polyvalent ions remaining in solution despite the pH adjustment, in particular the excess calcium ions used, and with sodium hydroxide solution and carbon dioxide and / or sodium carbonate and / or sodium bicarbonate adjusted to pH 8 to 12, preferably 9.0 to 11.0.
- the addition of carbon dioxide and / or sodium bicarbonate and / or sodium carbonate is carried out in an amount which has a concentration of carbonate ions in the amount of 0.01 to 0.18 mol / l, preferably 0.03 to 0.1 mol / l in the solution generated.
- the precipitation can also take place in several stages increasing amounts of sodium chromate are carried out.
- the precipitation of the calcium, the strontium and other polyvalent ions and surprisingly also the fluoride takes place, so that after the precipitation has been separated off, a sodium chromate solution with extremely low residual contents is present Contamination results.
- the sodium chromate solution produced in this way residual calcium and strontium contents of less than 5 mg / l are present, while other polyvalent cations such as barium, magnesium, iron, zinc and others as well as fluoride ions are no longer present or only in an amount of the respective detection limit, the detection limits being between 0.5 and 1 mg / l.
- the exchanger is to be regenerated by treatment with acid and is to be freed from the residues of the foreign anions introduced with the regenerating acid by washing with pure water and then to be converted into the sodium form with sodium hydroxide solution, so that the selective cation exchanger is then ready for use again.
- the various techniques for loading cation exchangers with the cations to be removed from solutions, for connecting and operating different exchange units in series or in parallel, and preferably for alternating regeneration, are known from the literature.
- the working temperature for the removal of the multivalent cations from the sodium chromate solution is 20 to 90 ° C., preferably 60 ° C to 85 ° C, the contact time of solution and exchanger is at least 2 min, preferably 6 min and more.
- the conversion of sodium chromate into sodium dichromate takes place in the process according to the invention with carbon dioxide.
- This so-called acidification of the sodium chromate can be carried out in one or more stages, and the first stage / the first stages can be operated without pressure;
- a carbon dioxide pressure of 4 to 15 bar, preferably 8 to 15 bar, at a final temperature below 50 ° C. is required in the last stage or in the last stages , preferably below 30 ° C.
- An at least 90% conversion of the sodium chromate at a pressure of more than 8 bar is preferred.
- the sodium bicarbonate obtained here can be converted into sodium carbonate, which is useful for chromium ore digestion, by thermal treatment and / or reaction with sodium hydroxide solution.
- a partial stream for the electrochemical generation of chromic acid is removed from the solution now present, which contains at least 80%, preferably at least 90%, of the chromium (VI) as dichromate and practically no longer contains polyvalent cations in detectable amounts.
- Another partial flow is used for the previously described pH adjustment during / after the leaching of the kiln goods.
- further parts of the solution of the preparation of sodium dichromate by adding sulfuric acid or by adding chromic acid or by adding chromic acid-sodium dichromate or by electrochemical acidification, as described, for example, in US Pat. No. 3,305,463 or as below for described the partial stream used for the production of chromic acid, which measures can also be taken simultaneously.
- the combination of electrochemical acidification with a simultaneous addition of dichromate-chromic acid solution in batches or continuously is a suitable method for complete conversion of the remaining sodium chromate to sodium dichromate in the non-chromic acid partial stream.
- the partial stream intended for this purpose is introduced into the anode chamber of a two-chamber electrolysis cell, the partition between the anode and cathode spaces of which is a cation-selective membrane, and therein into a solution which essentially contains sodium dichromate and only minor amounts of sodium chromate and / or chromic acid , electrolytically converted.
- a larger number of such electrolysis cells e.g. can be summarized in the manner of filter presses, operated in parallel.
- the voltage required to achieve a current density of 1 to 5 kA / m2, preferably 2.5 to 3.0 kA / m2, can either be applied individually to each cell which is electrically insulated from the other or, if the cells are conductively connected to one another, in a so-called bipolar circuit at the ends of such an electrically connected arrangement.
- the voltage to be applied is a function of the electrode spacing and the electrode construction, the solution temperature, the solution concentration and the current strength and is 3.8 to 6.0 V per electrolysis cell.
- Each electrolytic cell has in the anode compartment a feed line for the sodium chromate / sodium dichromate solution to be used and a drain for the electrolyzed solution essentially containing sodium dichromate.
- Supply and drain are usually against set ends of the respective electrolysis cell, the feed advantageously being in the lower part of the electrolysis cell and the outflow in the upper part of the electrolysis cell.
- the cathode chambers are equipped with inlet and outlet. Liquid is pumped both from the anode chamber and from the cathode chamber via external heat exchangers via separate openings in the frame of the cell or, as preferred, via the same openings as for the inlet and outlet.
- the streams to be pumped from the entirety of the anode chambers and the cathode chambers are advantageously combined to form an anolyte stream and a catholyte stream and are conducted via an anolyte cooler and a catholyte cooler. From these coolers, the cooled anolyte and catholyte liquids are again distributed to the individual anode and cathode chambers. By means of this cooling, the temperature in the anode compartment and cathode compartment is kept at 50 ° C. to 90 ° C., preferably 70 to 80 ° C.
- the electrolysis products oxygen and hydrogen are led out of anode spaces or cathode spaces via their own openings in the frame in the upper part of the cell and at the same time or exclusively via the same opening as the processes.
- the gas streams are advantageously brought together separately after the gases and, if appropriate, freed of entrained solutions and then used, for example, as heating and fuel material in the chrome ore digestion furnace.
- Water is entered into the cathode compartments either directly via the feed pipe or by adding to the catholyte liquid in the cooling circuit e.g. after catholyte cooler.
- the cathode liquid usually consists of 8 to 30%, preferably about 12 to 20% sodium hydroxide solution;
- the cathode compartment liquid can be modified if desired by adding agents which dull the alkali produced, for example carbon dioxide and / or sodium dichromate solution and / or sodium dichromate / sodium chromate solution from the aforementioned acidification with carbon dioxide.
- agents which dull the alkali produced for example carbon dioxide and / or sodium dichromate solution and / or sodium dichromate / sodium chromate solution from the aforementioned acidification with carbon dioxide.
- the concentration of the cathode compartment liquid can be adjusted via the water supply, it is preferably chosen to be as high as possible, restrictions mainly result from the membrane material used.
- Cation-selective membranes which can be used as partitions between the anode and cathode space in the two-room electrolysis cells in the process according to the invention, have already been described several times and have been on the market for a long time. Reinforced membranes with increased durability are preferred by incorporating fibers and fabrics. Both single-layer membranes and bimembranes, consisting of two different membrane types on top of one another, can be used, the two-layer membranes opposing the possible diffusion of hydroxide ions through the membrane with a higher resistance, thus offering the advantage of a higher current efficiency.
- suitable membranes have a perfluorocarbon polymer structure with sulfonate exchange groups
- suitable reinforcing materials are also fluorocarbon polymers, preferably polytetrafluoroethylene, they are commercially available, for example, under the names ®Nafion 324, Nafion 435, Nafion 430 and Nafion 423, from DuPont, UNITED STATES.
- the electrodes to be used on the cathode side are those that have already proven themselves in chlor-alkali electrolysis in the production of sodium hydroxide solution of various concentrations. They are usually made of steel, stainless steel or nickel and can be activated to reduce the overvoltage of the hydrogen.
- the electrodes to be used on the anode side must be resistant to the attack of the acidic and oxidizing medium and to the electrolytically generated oxygen. They consist of a titanium framework and are optionally coated after application of an intermediate oxide layer made of titanium oxide or tantalum oxide or tin oxide either wet-galvanized or melt-galvanized EP-A-0 356 804 or after the stoving process with platinum or with platinum / iridium with a predominant iridium content.
- the types of anodes that can be used are those that have proven themselves in other gas-generating processes, for example anodes in perforated plate shapes, expanded metal anodes, knife anodes, spaghetti anodes and blind anodes.
- the distance between the electrodes is chosen to be as small as possible, preferably less than 10 mm.
- Materials that are resistant to sodium dichromate in particular titanium and post-chlorinated PVC, are suitable as construction material for the electrolysis cells.
- the degrees of conversion of sodium dichromate to chromic acid in the individual stages are such that in the last stage a conversion to 55 to 70%, preferably 59 to 65%, has taken place, so that a Sodium ion: chromic acid ratio of 0.45: 0.55 to 0.30: 0.70, preferably from 0.41: 0.59 to 0.35: 0.65, particularly preferably 0.4: 0.6 .
- the electrolysis cells used for this conversion in all stages are similar to those described in the last section for converting the sodium chromate / sodium dichromate solution into a solution essentially containing sodium dichromate, and they are preferably set up and operated together with them , so that their current and voltage supply as well as their hydrogen and oxygen cleaning and disposal as well as their cathode room liquid treatment, their cooling and concentration and disposal can be summarized.
- the same monopolar or bipolar current and voltage supply is selected, the current density here too is 1 to 5 kA / m2, preferably 2.5 to 3.0 kA / m2, and the voltage to be applied per electrolysis cell is 3.8 to 6.0 Volt; higher voltages are possible, but are avoided for economic as well as technical reasons.
- the product of the respective previous stage is fed to the electrolytic cells via the feed line of the anode chambers, and the product is fed to the next stage in each case via the outlet.
- the anolytes are collected for each stage and passed over a heat exchanger for the purpose of heat dissipation and fed back cooled on the opposite side of the anode chamber in the lower part.
- the total number of heat exchangers for anolytes is therefore equal to the number of electrolysis stages.
- the catholytes can be combined for all stages and are then preferred together wise combined with the cathode liquid from the step described above of converting sodium chromate / sodium dichromate into sodium dichromate solution, cooled and then redistributed to the individual cathode compartments.
- cathode compartment fluid is removed from the circuit and fed to further processing, for example by concentration.
- a preferred form of further processing is evaporation in a vacuum in one to three evaporator stages using the heat released during the electrolysis, so that at least some of the heat exchangers with which the electrolytic heat is removed from the catholyte liquid are identical to some of the heat exchangers for the evaporation of the removed cathode compartment liquid.
- the composition of the cathode compartment liquid is the same as that of the previous step of converting sodium chromate / sodium dichromate solution to sodium dichromate solution.
- the temperatures of the solutions in the electrolysis cells are 50 to 90 ° C., preferably 70 to 80 ° C. in all stages.
- Membranes to be used, anodes, cathodes and construction materials are the same as described above.
- the function of the cells can be changed at certain time intervals that they realize another sodium dichromate-chromic acid conversion step by changing the flow direction of the anode chamber liquids.
- the electrolysis stage with the highest degree of conversion to chromic acid can take over the function of the stage with the lowest degree of conversion and vice versa.
- each cell arrangement can thus take over the function of each electrolysis stage in chronological order.
- the anode chamber liquid removed from the last stage of the multi-stage electrolysis is fed to a one to three stage evaporation, the last evaporation stage being designed as an evaporation crystallizer. It is evaporated to such an extent that a crystallization of chromic acid takes place when the solubility limit is exceeded. It is preferably evaporated to a water content in the mixture of 9 to 20% by weight, particularly preferably to a water content of 12 to 15% by weight.
- the temperature to be set in the crystallizer is 50 to 110 ° C., preferably 55 to 80 ° C., particularly preferably approx. 60 ° C.
- Crystallizers or crystallization evaporators with an internal heating chamber or with an external heating circuit are suitable for the preferably continuous crystallization. In any case, they must be operated at reduced pressure, so that the evaporation can be carried out at the above temperatures.
- Crystallizers made of titanium are preferably used, which make it possible to produce crystals free of fine grains, that is to say those in whose operation the crystal suspension is screened at least partially according to the crystal size; these are so-called FC (forced circulation) crystallizers and also guide tube crystallizers, for example in combination with hydrocyclones or settling tanks / tanks; Guide tube crystallizers with a clarification zone are even more suitable, e.g. double propeller (DP) crystallizers and fluidized bed crystallizers (see W. Woehlk, G. Hofmann, International Chem. Engineering 27 , 197 (1987); RC Bennett, Chemical Engineering 1988, p. 119 ff).
- DP double propeller
- the crystal sludge removed from the crystallizer can be further thickened via a liquid cyclone (hydrocyclone) or settling container and is either placed directly or after thickening on a centrifuge which is made of titanium in its parts in contact with liquids.
- the liquid is spun off the crystal cake as far as possible and then the crystal cake is washed one or more times, preferably one to three times, with saturated or almost saturated chromic acid solution.
- the saturated or almost saturated chromic acid solution can be obtained outside the centrifuge by dissolving chromic acid, preferably by dissolving a portion of the purified chromic acid in the form of the moist, washed filter cake and / or by dissolving an intended fraction of fine particles from the crystalline product dried in the last process step
- Chromic acid can be produced, but can also be generated in the centrifuge itself by spraying or spraying water or dilute chromic acid solution onto the filter cake.
- the total amount of water to be used for the washing process is between 3 and 25% by weight, based on the moist centrifuge cake (filter cake), preferably between 4 and 10% by weight, this amount of water is used as such or in the form of a chromic acid solution either all at once or added in portions to the filter cake to be washed out.
- washing solution is added in several portions, the resulting solutions running out of the filter cake can be combined or collected separately; in the case of separate pick-up, it is possible to use the processes which are contaminated differently and decreasing from washing step to washing step again in the next centrifuging cycle as washing solution for the respective preceding washing stages.
- the sequence from the first washing step after centrifuging off the mother liquor or, in the case of single-stage cake washing, the entire washing liquid running off is fed to the evaporation crystallizer, the temperature of the solution being maintained or increased along the way.
- the mother liquor of the chromic acid crystallization flowing out of the centrifuge which is saturated or slightly supersaturated in chromic acid, is mostly fed to the anode side of the multi-stage electrolysis of sodium dichromate to chromic acid without further cooling.
- the mother liquor, the composition of sodium dichromate and chromic acid, is converted to a degree of conversion 50% of the sodium dichromate in chromic acid corresponds to the level selected among the electrolysis levels that most closely corresponds to the degree of conversion according to the incoming mother liquor.
- the applicable electrolysis level can be determined mathematically and / or experimentally.
- the fourth electrolysis stage is suitable, for example, for absorbing the mother liquor in an eight-stage system, whereas the fifth electrolysis stage in an eleven-stage system .
- water can be added to the mother liquor before it enters electrolysis, or the corresponding amount of water can be fed directly into the anode chambers or the associated cooling circuit for the anode liquid. Any amount of water added is limited so that the water content of the resulting solution does not exceed 50% by weight, that is to say between 25 and 50% by weight.
- a small part of the mother liquor flowing out of the centrifuge is fed into the upstream acidification stages for the removal of impurities which have been introduced into the electrolysis circuit, i.e. either into the partial stream removed in process step 7 for the pH adjustment in step 1 or else, as preferred, in the partial stream withdrawn in step 7 for the production of sodium dichromate.
- the discharged solution runs through again all the cleaning steps listed to remove accumulated impurities, in the second case the discharged solution completely leaves the chromic acid production process. If one speaks of the smaller part of the mother liquor flowing out of the centrifuge, then the smaller part in the long-term average is referred to.
- short-term is considered to be a period of time that does not exceed approximately thirty times the period in which the average volume of sodium dichromate solution flowing from step 7 of the multi-stage electrolysis is the total anode liquid volume of the multi-stage electrolysis including cooling circuits and the crystallizer and the stack container possibly installed in this anode liquid flow.
- Preference over the unevenly timed removal of mother liquor is the timely even removal of a small part of the mother liquor into the streams of sodium dichromate solution, which are used for producing sodium dichromate or for adjusting the pH in step 1.
- a small part of the mother liquor is to be understood as meaning a part which contains between 2% and 20%, preferably between 5% and 10%, of the molar amount of chromium (VI) which is introduced from step 7 into the multi-stage electrolysis.
- the pure, crystalline, moisture-laden chromic acid generated in step 12 can be converted into salable goods in different ways after removal or ejection from the centrifuge. If a chromic acid solution generated outside the centrifuge is used to wash the chromic acid crystals in step 12, this moist chromic acid crystal cake is well suited for this and a corresponding proportion is removed. A commercially available, very pure chromic acid solution can also be prepared from the moist crystal cake without further treatment. In order to obtain dry, crystalline goods, the water must be removed below the chromic acid decomposition temperature, that is to say in the temperature range below 195 ° C., preferably from 165 to 185 ° C.
- the drying can be followed by a dedusting by screening or classifying in order to remove dusty or finely crystalline fractions, wherein the fine material which has been envisaged can be used to prepare chromic acid solution for washing the thrown off chromic acid crystals in the centrifuge in step 12.
- the gases produced during the electrolysis, oxygen in the anode chamber and hydrogen in the cathode chamber are each drawn off individually from the electrolysis chambers, normally from the upper part of the electrolysis cell and together with the respective anode chamber liquid or cathode chamber liquid.
- the gas streams can, for example, be washed with water or passed over so-called droplet separators or mist separators.
- contacting the oxygen stream with an absorbent reactive towards chlorine for example aqueous sodium hydroxide solution and moist activated carbon, is recommended.
- both the oxygen and the hydrogen are fed into the chrome ore digestion furnace in separate lines as oxidizing agent or as fuel.
- a sodium alkali product is formed in the cathode compartments in addition to hydrogen, from the hydroxide ions generated at the cathode and from Anode spaces immigrated over the cation-selective membranes, as already described above.
- the sodium alkali product from the cathode compartments is preferably used for the production of solid sodium carbonate for chromium ore digestion and as a conditioning agent for the chromium ore residue and for sodium chromate solution.
- Intermediate stages on the way to solid sodium carbonate can be: dilute and concentrated sodium hydroxide solution, sodium carbonate solution, sodium bicarbonate.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Automation & Control Theory (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE3829121 | 1988-08-27 | ||
DE3829121A DE3829121A1 (de) | 1988-08-27 | 1988-08-27 | Elektrochemisches verfahren zur herstellung von chromsaeure |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0356802A2 EP0356802A2 (de) | 1990-03-07 |
EP0356802A3 EP0356802A3 (en) | 1990-05-16 |
EP0356802B1 true EP0356802B1 (de) | 1992-07-29 |
Family
ID=6361721
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP89115030A Expired - Lifetime EP0356802B1 (de) | 1988-08-27 | 1989-08-15 | Elektrochemisches Verfahren zur Herstellung von Chromsäure |
Country Status (15)
Country | Link |
---|---|
US (1) | US5068015A (es) |
EP (1) | EP0356802B1 (es) |
JP (1) | JP2812730B2 (es) |
KR (1) | KR0152524B1 (es) |
AR (1) | AR247252A1 (es) |
BR (1) | BR8904252A (es) |
CA (1) | CA1338145C (es) |
DD (1) | DD284060A5 (es) |
DE (2) | DE3829121A1 (es) |
ES (1) | ES2042904T3 (es) |
MX (1) | MX170481B (es) |
PL (1) | PL163883B1 (es) |
RO (1) | RO107136B1 (es) |
TR (1) | TR24735A (es) |
ZA (1) | ZA896495B (es) |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6063252A (en) * | 1997-08-08 | 2000-05-16 | Raymond; John L. | Method and apparatus for enriching the chromium in a chromium plating bath |
CN103668301B (zh) * | 2013-12-11 | 2016-08-24 | 中国科学院青海盐湖研究所 | 利用电解法制备铬酸钠溶液的装置和方法 |
CN108103521B (zh) * | 2017-12-22 | 2019-10-15 | 四川省银河化学股份有限公司 | 一种提高电解法制备铬酸酐品质的方法 |
CN113184907A (zh) * | 2021-05-31 | 2021-07-30 | 河钢承德钒钛新材料有限公司 | 一种铬酸钠的纯化方法 |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0356804A2 (de) * | 1988-08-27 | 1990-03-07 | Bayer Ag | Verfahren zur Herstellung von Alkalidichromaten und Chromsäure |
EP0356803A2 (de) * | 1988-08-27 | 1990-03-07 | Bayer Ag | Verfahren zur Herstellung eines Elektrolyten zur Erzeugung von Alkalidichromaten und Chromsäure |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CA739447A (en) * | 1966-07-26 | W. Carlin William | Electrolytic production of chromic acid | |
US3046091A (en) * | 1958-12-19 | 1962-07-24 | Pittsburgh Plate Glass Co | Preparation of alkali metal dichromate |
US3305463A (en) * | 1962-03-16 | 1967-02-21 | Pittsburgh Plate Glass Co | Electrolytic production of dichromates |
US3454478A (en) * | 1965-06-28 | 1969-07-08 | Ppg Industries Inc | Electrolytically reducing halide impurity content of alkali metal dichromate solutions |
-
1988
- 1988-08-27 DE DE3829121A patent/DE3829121A1/de not_active Withdrawn
-
1989
- 1989-08-07 MX MX017095A patent/MX170481B/es unknown
- 1989-08-10 RO RO141223A patent/RO107136B1/ro unknown
- 1989-08-15 US US07/393,733 patent/US5068015A/en not_active Expired - Lifetime
- 1989-08-15 EP EP89115030A patent/EP0356802B1/de not_active Expired - Lifetime
- 1989-08-15 DE DE8989115030T patent/DE58901937D1/de not_active Expired - Lifetime
- 1989-08-15 ES ES89115030T patent/ES2042904T3/es not_active Expired - Lifetime
- 1989-08-22 TR TR89/0673A patent/TR24735A/xx unknown
- 1989-08-24 BR BR898904252A patent/BR8904252A/pt not_active IP Right Cessation
- 1989-08-24 JP JP1216185A patent/JP2812730B2/ja not_active Expired - Lifetime
- 1989-08-25 PL PL89281165A patent/PL163883B1/pl unknown
- 1989-08-25 DD DD89332098A patent/DD284060A5/de not_active IP Right Cessation
- 1989-08-25 ZA ZA896495A patent/ZA896495B/xx unknown
- 1989-08-25 AR AR89314751A patent/AR247252A1/es active
- 1989-08-25 CA CA000609439A patent/CA1338145C/en not_active Expired - Fee Related
- 1989-08-26 KR KR1019890012190A patent/KR0152524B1/ko not_active IP Right Cessation
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0356804A2 (de) * | 1988-08-27 | 1990-03-07 | Bayer Ag | Verfahren zur Herstellung von Alkalidichromaten und Chromsäure |
EP0356803A2 (de) * | 1988-08-27 | 1990-03-07 | Bayer Ag | Verfahren zur Herstellung eines Elektrolyten zur Erzeugung von Alkalidichromaten und Chromsäure |
Also Published As
Publication number | Publication date |
---|---|
EP0356802A2 (de) | 1990-03-07 |
MX170481B (es) | 1993-08-25 |
ZA896495B (en) | 1990-05-30 |
DD284060A5 (de) | 1990-10-31 |
KR900003418A (ko) | 1990-03-26 |
PL163883B1 (pl) | 1994-05-31 |
JPH02104684A (ja) | 1990-04-17 |
BR8904252A (pt) | 1990-04-10 |
US5068015A (en) | 1991-11-26 |
JP2812730B2 (ja) | 1998-10-22 |
RO107136B1 (ro) | 1993-09-30 |
TR24735A (tr) | 1992-03-06 |
AR247252A1 (es) | 1994-11-30 |
KR0152524B1 (ko) | 1998-10-15 |
DE3829121A1 (de) | 1990-03-01 |
DE58901937D1 (de) | 1992-09-03 |
ES2042904T3 (es) | 1993-12-16 |
EP0356802A3 (en) | 1990-05-16 |
CA1338145C (en) | 1996-03-12 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
DE3032875A1 (de) | Verfahren zur chloralkali-elektrolyse | |
DE69200006T2 (de) | Verfahren zur elektrolytischen Herstellung von Alkalimetall-Chlorat und chemische Hilfsverbindungen. | |
DE2419690C3 (de) | Verfahren zur Entfernung von Dichromaten aus bei der Elektrolyse anfallenden, mit Chloraten angereicherten Alkalimetallchlorat-Alkalimetallchloridlösungen | |
DE3020260C2 (es) | ||
DE1814027A1 (de) | Kontinuierliches Verfahren zur Absorption und Gewinnung von sauren Gasen und dafuer geeignete Vorrichtung | |
DE1916491A1 (de) | Verfahren zur Gewinnung saurer Gase aus Abgasen | |
DE69601110T2 (de) | Auslaugungsverfahren | |
EP0599136B1 (de) | Verfahren zur Herstellung von reinem Nickelhydroxid sowie dessen Verwendung | |
EP0391192B1 (de) | Verfahren zur Herstellung von Alkalidichromaten und Chromsäuren durch Elektrolyse | |
DE10106932A1 (de) | Verfahren zur Herstellung von Natriumpersulfat | |
EP0356802B1 (de) | Elektrochemisches Verfahren zur Herstellung von Chromsäure | |
DE2432416A1 (de) | Verfahren zur gewinnung von elektrolytisch hergestellten alkalichloraten | |
WO1988007975A1 (en) | Process for reducing the impurities in lyes in the bayer process | |
DE3834807A1 (de) | Verfahren zur herstellung von kohlensauren salzen von alkalimetallen | |
DE3020280A1 (de) | Verfahren zur herstellung von chromsaeure in einer dreiraum-zelle | |
DE2124045C3 (de) | Verfahren zur elektrolytischen Her stellung von reinem Chlor, Wasserstoff und reinen konzentrierten Alkaliphosphat lösungen und Elektrolyslerzelle zur Durch führung des Verfahrens | |
DE19858544A1 (de) | Verfahren zur Herstellung von Natriumpersulfat | |
EP0011886B1 (de) | Verfahren zur elektrolytischen Gewinnung von Chlorsauerstoffsäuren bzw. deren Salze | |
DE4119606A1 (de) | Verfahren und vorrichtung zur aufarbeitung von salzsaeurehaltigem, mit begleitstoffen verunreinigtem wasser | |
EP0368066B1 (de) | Verfahren zur Herstellung von Natriumdichromat | |
DE69506526T2 (de) | Verfahren zur herstellung hypophosphoriger säure | |
DE4033489C2 (es) | ||
DE19516304C1 (de) | Verfahren zur Herstellung von Alkaliperoxid-Hydrat | |
DE1106301B (de) | Kreislaufverfahren zur Herstellung von Kaliumpermanganat | |
DE3314877A1 (de) | Verfahren zur behandlung einer entnahmeloesung, insbesondere fuer ein zinkextraktionsverfahren auf elektrolytischem weg |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
17P | Request for examination filed |
Effective date: 19890815 |
|
AK | Designated contracting states |
Kind code of ref document: A2 Designated state(s): DE ES FR GB IT |
|
PUAL | Search report despatched |
Free format text: ORIGINAL CODE: 0009013 |
|
AK | Designated contracting states |
Kind code of ref document: A3 Designated state(s): DE ES FR GB IT |
|
17Q | First examination report despatched |
Effective date: 19911217 |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): DE ES FR GB IT |
|
ET | Fr: translation filed | ||
ITF | It: translation for a ep patent filed | ||
REF | Corresponds to: |
Ref document number: 58901937 Country of ref document: DE Date of ref document: 19920903 |
|
GBT | Gb: translation of ep patent filed (gb section 77(6)(a)/1977) | ||
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
26N | No opposition filed | ||
REG | Reference to a national code |
Ref country code: ES Ref legal event code: FG2A Ref document number: 2042904 Country of ref document: ES Kind code of ref document: T3 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 19960729 Year of fee payment: 8 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: ES Payment date: 19960807 Year of fee payment: 8 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: ES Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 19970816 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 19980430 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: ST |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: IF02 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20020711 Year of fee payment: 14 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 20030813 Year of fee payment: 15 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20040302 |
|
REG | Reference to a national code |
Ref country code: ES Ref legal event code: FD2A Effective date: 19980910 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GB Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20040815 |
|
GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 20040815 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED. Effective date: 20050815 |