CN113387407A - Method for separating and recovering cadmium from base metal solution - Google Patents
Method for separating and recovering cadmium from base metal solution Download PDFInfo
- Publication number
- CN113387407A CN113387407A CN202110661070.1A CN202110661070A CN113387407A CN 113387407 A CN113387407 A CN 113387407A CN 202110661070 A CN202110661070 A CN 202110661070A CN 113387407 A CN113387407 A CN 113387407A
- Authority
- CN
- China
- Prior art keywords
- solution
- cadmium
- anion exchanger
- base metal
- strongly basic
- 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.)
- Pending
Links
- 229910052793 cadmium Inorganic materials 0.000 title claims abstract description 167
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 title claims abstract description 167
- 238000000034 method Methods 0.000 title claims abstract description 99
- 239000010953 base metal Substances 0.000 title claims abstract description 95
- 150000001450 anions Chemical class 0.000 claims abstract description 92
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 56
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 54
- 239000011701 zinc Substances 0.000 claims abstract description 54
- 238000003795 desorption Methods 0.000 claims abstract description 22
- 238000011084 recovery Methods 0.000 claims abstract description 22
- 125000005843 halogen group Chemical group 0.000 claims abstract description 21
- 239000000243 solution Substances 0.000 claims description 258
- 238000001179 sorption measurement Methods 0.000 claims description 66
- 239000007864 aqueous solution Substances 0.000 claims description 56
- 239000003957 anion exchange resin Substances 0.000 claims description 49
- 229910052736 halogen Inorganic materials 0.000 claims description 41
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 38
- -1 halogen ions Chemical class 0.000 claims description 38
- 150000002367 halogens Chemical class 0.000 claims description 24
- 230000008569 process Effects 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 20
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 19
- 239000000835 fiber Substances 0.000 claims description 18
- 238000005349 anion exchange Methods 0.000 claims description 17
- WLZRMCYVCSSEQC-UHFFFAOYSA-N cadmium(2+) Chemical compound [Cd+2] WLZRMCYVCSSEQC-UHFFFAOYSA-N 0.000 claims description 17
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 16
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 15
- 150000003242 quaternary ammonium salts Chemical group 0.000 claims description 15
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 13
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 12
- 238000010828 elution Methods 0.000 claims description 12
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 11
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 235000019270 ammonium chloride Nutrition 0.000 claims description 8
- 239000001103 potassium chloride Substances 0.000 claims description 8
- 235000011164 potassium chloride Nutrition 0.000 claims description 8
- 239000011780 sodium chloride Substances 0.000 claims description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 7
- 229920006395 saturated elastomer Polymers 0.000 claims description 6
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- 239000003011 anion exchange membrane Substances 0.000 claims description 2
- XZUAPPXGIFNDRA-UHFFFAOYSA-N ethane-1,2-diamine;hydrate Chemical compound O.NCCN XZUAPPXGIFNDRA-UHFFFAOYSA-N 0.000 claims description 2
- 238000000926 separation method Methods 0.000 abstract description 13
- 230000008901 benefit Effects 0.000 abstract description 9
- 239000003440 toxic substance Substances 0.000 abstract description 6
- 230000007613 environmental effect Effects 0.000 abstract description 5
- 238000003912 environmental pollution Methods 0.000 abstract description 4
- 238000002336 sorption--desorption measurement Methods 0.000 abstract description 3
- 231100000167 toxic agent Toxicity 0.000 abstract 1
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 27
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 22
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 18
- 229910052802 copper Inorganic materials 0.000 description 18
- 239000010949 copper Substances 0.000 description 18
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 18
- 229910000368 zinc sulfate Inorganic materials 0.000 description 18
- 229960001763 zinc sulfate Drugs 0.000 description 18
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 16
- 229910001385 heavy metal Inorganic materials 0.000 description 14
- 239000002351 wastewater Substances 0.000 description 14
- 229910052751 metal Inorganic materials 0.000 description 12
- 229910052742 iron Inorganic materials 0.000 description 11
- 238000003756 stirring Methods 0.000 description 10
- 238000005406 washing Methods 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- 229910052740 iodine Inorganic materials 0.000 description 9
- 239000011630 iodine Substances 0.000 description 9
- 229910052759 nickel Inorganic materials 0.000 description 8
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 7
- 239000000460 chlorine Substances 0.000 description 7
- 229910052801 chlorine Inorganic materials 0.000 description 7
- 238000001914 filtration Methods 0.000 description 7
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 150000001768 cations Chemical class 0.000 description 6
- 239000010941 cobalt Substances 0.000 description 6
- 229910017052 cobalt Inorganic materials 0.000 description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 6
- 239000000839 emulsion Substances 0.000 description 6
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 6
- 229910052753 mercury Inorganic materials 0.000 description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 6
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 5
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 5
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 5
- 229910052794 bromium Inorganic materials 0.000 description 5
- 229910000365 copper sulfate Inorganic materials 0.000 description 5
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 5
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 5
- 231100000614 poison Toxicity 0.000 description 5
- 229910001414 potassium ion Inorganic materials 0.000 description 5
- 238000010923 batch production Methods 0.000 description 4
- 238000010924 continuous production Methods 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 4
- 239000002893 slag Substances 0.000 description 4
- 230000003068 static effect Effects 0.000 description 4
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 3
- 229910000011 cadmium carbonate Inorganic materials 0.000 description 3
- GKDXQAKPHKQZSC-UHFFFAOYSA-L cadmium(2+);carbonate Chemical compound [Cd+2].[O-]C([O-])=O GKDXQAKPHKQZSC-UHFFFAOYSA-L 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 125000001453 quaternary ammonium group Chemical group 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 229910001415 sodium ion Inorganic materials 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- 239000011592 zinc chloride Substances 0.000 description 3
- 235000005074 zinc chloride Nutrition 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- CXKCTMHTOKXKQT-UHFFFAOYSA-N cadmium oxide Inorganic materials [Cd]=O CXKCTMHTOKXKQT-UHFFFAOYSA-N 0.000 description 2
- CFEAAQFZALKQPA-UHFFFAOYSA-N cadmium(2+);oxygen(2-) Chemical compound [O-2].[Cd+2] CFEAAQFZALKQPA-UHFFFAOYSA-N 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 238000007667 floating Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000010842 industrial wastewater Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 230000000813 microbial effect Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000001698 pyrogenic effect Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 239000002956 ash Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000011549 displacement method Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 229910001447 ferric ion Inorganic materials 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 230000003100 immobilizing effect Effects 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000005375 photometry Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 125000001302 tertiary amino group Chemical group 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/34—Regenerating or reactivating
- B01J20/345—Regenerating or reactivating using a particular desorbing compound or mixture
- B01J20/3475—Regenerating or reactivating using a particular desorbing compound or mixture in the liquid phase
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B17/00—Obtaining cadmium
- C22B17/04—Obtaining cadmium by wet processes
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/16—Regeneration of sorbents, filters
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Materials Engineering (AREA)
- Water Supply & Treatment (AREA)
- Environmental & Geological Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Hydrology & Water Resources (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Treatment Of Water By Ion Exchange (AREA)
- Electrolytic Production Of Metals (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention provides a method for separating and recovering cadmium from a base metal solution, which comprises the following steps: (1) adsorbing a base metal solution containing cadmium by using a strongly basic anion exchanger containing halogen groups to obtain an adsorbed strongly basic anion exchanger; (2) when the base metal solution containing cadmium contains zinc, eluting the adsorbed strong-base anion exchanger by using a first solution to obtain a zinc-containing solution and a zinc-desorbed strong-base anion exchanger; eluting the zinc desorption strong-base anion exchanger by using a second solution to obtain a cadmium-containing solution; or when the base metal solution containing cadmium does not contain zinc, eluting the adsorbed strong-base anion exchanger by a second solution to obtain the solution containing cadmium. The invention realizes the separation and recovery of cadmium in the base metal solution by adopting an adsorption-desorption method, has simple operation, low treatment cost, no toxic substance participation, no environmental pollution and good environmental benefit and economic benefit.
Description
Technical Field
The invention relates to the technical field of metallurgy and environmental protection, in particular to a method for separating and recovering cadmium from base metal solution.
Background
The problems of cadmium removal or separation of cadmium from other metal elements are often involved in the smelting of base metals (such as manganese, cobalt, nickel, copper, zinc, etc.) from natural minerals or renewable resources and in the removal or recovery of heavy metals from wastewater. Conventional cadmium removal techniques include pyrogenic and wet processes. Pyrogenic processes separate cadmium from other metals by high temperature distillation, for example, separation of cadmium from zinc is often pyrogenically used. The method has high energy consumption and pollution, is still widely applied, but is not in accordance with the modern development concept. The classic wet cadmium removing method is a displacement method, in particular to the removal of cadmium in zinc salt, namely, cadmium ions are reduced into metal cadmium by zinc ash (pure zinc powder) under the weak acid condition, and cadmium slag formed by the metal cadmium and excessive zinc is removed by filtration. The method needs to consume a large amount of pure zinc powder, needs to strictly control the acidity of the solution, needs highly toxic antimony as an accelerant, and needs to further separate and purify the obtained cadmium slag mixture if the cadmium slag mixture needs to be recycled. In recent years, many researches on extraction and separation of cadmium by using solvents have appeared, but the used extracting agents are often high-toxicity compounds, the extraction conditions are harsh, the separation effect is not ideal, and the problems of environmental pollution caused by loss of the extracting agents and the solvents exist.
CN112429888A discloses a method for recycling cadmium-containing heavy metal wastewater, which is to add ammonium carbonate or sodium carbonate into cadmium-containing heavy metal wastewater to generate cadmium carbonate precipitate from cadmium, and then wash the precipitate with nitric acid to remove impurities such as calcium, magnesium, nickel, iron and the like, thereby improving the purity of cadmium oxide generated after the cadmium carbonate is thermally treated. The generated cadmium oxide can be used for cyaniding cadmium plating solution, thereby realizing the recovery and resource utilization of cadmium in the cadmium-containing wastewater. And removing heavy metal ions from the settled clear liquid through electric flocculation and then recycling the settled clear liquid. The method recycles the cadmium element in the cadmium-containing wastewater, and achieves the purpose of recycling. However, in the method, impurities such as calcium, magnesium, nickel, iron and the like in the precipitate are removed by washing with nitric acid, a large amount of acidic wastewater is generated, and secondary pollution is caused to the environment.
CN109052620A discloses a method for removing cadmium ions in heavy metal wastewater, the method utilizes electric energy generated by degrading organic matters by a microbial fuel cell to drive a microbial electrolytic cell to treat the cadmium-containing heavy metal wastewater, external electric energy is not consumed in the whole process, secondary pollution is not generated, and the method is an environment-friendly novel method for treating the cadmium-containing heavy metal wastewater. The method comprises the following three steps: 1. determining MFC operating parameters; 2. constructing an MFC-MEC self-driven coupling system; 3. treatment of cadmium-containing heavy metal wastewater: through the steps 1 and 2, the wastewater containing the cadmium and the heavy metal is treated by using MEC cathode reaction, the catholyte is the wastewater containing the cadmium and the heavy metal, the pH value is 1-5, the anode is made of carbon paper, and the cathode material is made of stainless steel, a titanium plate and carbon paper. And after the MEC reaction is finished, taking out the cathode, collecting the MEC cathode reduction product, and detecting by XRD (X-ray diffraction), wherein the MEC cathode product is cadmium carbonate, and the removal rate of cadmium ions is 89.5%. However, the method utilizes microorganisms to degrade organic matters to provide electric energy, the generated current is small, the required treatment time is long, and the treatment effect is unstable.
CN1194238A discloses a method for removing heavy metals from industrial wastewater, which comprises the steps of directly contacting and adsorbing the industrial wastewater containing heavy metals such as copper, zinc, chromium, cadmium, nickel, lead and the like with coal slag particles and fly ash of industrial wastes, and discharging after solid-liquid separation. However, the method has poor effect of removing heavy metals, produces a large amount of waste residues, and does not separate cadmium from other metal elements.
CN102464396A discloses a method for treating cadmium-containing wastewater, which comprises the following steps: (1) preparing an emulsion from a foaming agent, an organic solvent and an auxiliary agent; (2) immobilizing the emulsion prepared above on a carrier; (3) adding the prepared substances into cadmium-containing wastewater, adjusting the pH to 3.0-6.5 by using acid, and stirring at the rotating speed of 100-450 r/min; (4) standing for 2-10 min, floating the emulsion, demulsifying the floating emulsion through a high-voltage electric field to recover heavy metal cadmium, and returning the obtained oil phase to the emulsion maker to circularly make emulsion; the effluent can be lower than the national first-grade discharge standard. However, the method needs high-voltage electric field demulsification, has high treatment cost and does not separate cadmium from other metal elements.
Therefore, the development of a method for realizing the high-efficiency separation of cadmium and other metal elements in the solution, which has low treatment cost, no toxic substances and no waste residue has important significance.
Disclosure of Invention
In view of the problems in the prior art, the invention provides a method for separating and recovering cadmium from a base metal solution, which adopts an adsorption-desorption method to separate and recover cadmium in the base metal solution, the obtained cadmium-containing solution does not contain other metal elements, the cadmium can be directly recovered without secondary separation, the treatment cost is low, toxic substances are not used, waste residues are not generated, and the method has good economic benefit and environmental benefit.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a method for separating and recovering cadmium from a base metal solution, which comprises the following steps:
(1) adsorbing a base metal solution containing cadmium by using a strongly basic anion exchanger containing halogen groups to obtain an adsorbed strongly basic anion exchanger;
(2) when the base metal solution containing cadmium contains zinc, eluting the adsorbed strong-base anion exchanger by using a first solution to obtain a zinc-containing solution and a zinc-desorbed strong-base anion exchanger; eluting the zinc desorption strong-base anion exchanger by using a second solution to obtain a cadmium-containing solution;
or when the base metal solution containing cadmium does not contain zinc, eluting the adsorbed strong-base anion exchanger by a second solution to obtain the solution containing cadmium.
The method adopts a strong-base anion exchanger containing halogen groups to selectively and stably adsorb cadmium ions in a base metal solution, and then uses a second solution for elution to obtain a cadmium-containing solution. Considering that the zinc ions in the base metal solution affect the purity of cadmium, when the base metal solution contains zinc, the first solution is used for selectively desorbing the zinc ions, and then the second solution is used for eluting the cadmium to obtain the cadmium-containing solution. The method has the advantages of simple operation, low treatment cost, no use of toxic substances and good industrial application prospect.
After the adsorption in the step (1) of the invention, the base metal solution after adsorption is generated, and the base metal solution after cadmium removal can be further treated to recover base metal elements in the base metal solution.
The zinc-containing solution in step (2) of the present invention can also be subjected to zinc recovery.
Preferably, the preparation method of the halogen group-containing strongly basic anion exchanger of step (1) comprises: and adsorbing the halogen ions in the halogen solution by using the strong-base anion exchanger to obtain the strong-base anion exchanger containing the halogen groups.
In the invention, if the chlorine type strong-base anion exchanger is adopted, the commercial chlorine type strong-base anion exchanger can be directly used without preparation. However, the invention adopts strong alkaline anion exchanger containing bromine or iodine to adsorb cadmium in base metal solution with better effect.
In the invention, the excessive halogen solution is needed to realize the saturated adsorption of the strong-base anion exchanger, so the mass ratio of the strong-base anion exchanger to the halogen solution is not limited. The strongly basic anion exchanger saturated by adsorption is washed by pure water to remove the excessive halogen solution.
Preferably, the process for the preparation of the strongly basic anion exchanger comprises a static process or a dynamic process.
The static method of the invention comprises mixing a strong base anion exchanger and a halogen solution, and carrying out standing adsorption.
Preferably, the dynamic process comprises a batch process or a continuous process.
Preferably, the batch process comprises a stirred process.
The stirring method of the invention comprises stirring and mixing the strong-base anion exchanger and the halogen solution for adsorption.
Preferably, the continuous process comprises a column-crossing process.
The column passing method comprises the steps of filling a strong-base anion exchanger into an adsorption column, and enabling a halogen solution to flow through the adsorption column for adsorption.
Preferably, the anion in the halogen solution comprises any one of chloride, bromide or iodide or a combination of at least two thereof, wherein typical but non-limiting combinations include a combination of chloride and bromide, bromide and iodide or a combination of chloride, bromide and iodide.
Preferably, the cations in the halogen solution include any one or a combination of at least two of sodium ions, potassium ions, ammonium ions, hydrogen ions, magnesium ions, or calcium ions, wherein typical but non-limiting combinations include a combination of sodium ions and potassium ions, a combination of potassium ions and ammonium ions, a combination of ammonium ions and hydrogen ions, a combination of hydrogen ions, potassium ions, and sodium ions, or a combination of hydrogen ions, ammonium ions, and potassium ions.
The cation of the halogen solution in the present invention may be other monovalent cation or divalent cation.
Preferably, the concentration of the anion in the halogen solution is 0.001mM to 10M, and may be, for example, 0.001mM, 0.01mM, 5mM, 1M, 3M, 5M, 8M, or 10M.
Preferably, the halogen solution has a pH of 0.1 to 10, and may be, for example, 0.1, 0.5, 1, 3, 5, 7, 9 or 10.
Preferably, the strongly basic anion exchanger in step (1) comprises any one of strongly basic anion exchange resin, strongly basic anion exchange fiber or strongly basic anion exchange membrane, preferably strongly basic anion exchange fiber.
The invention preferably uses strong base anion exchange fiber to absorb halogen ion because the functional group of the strong base anion exchange fiber is on the surface of the fiber, without the need of the process of diffusion in the particle, the mass transfer rate is fast, and the absorption effect to cadmium ion in base metal solution is good.
The strongly basic anion exchangers used in the present invention can have different particle sizes and different pore sizes, and any of those well known to those skilled in the art can be used to achieve adsorptive separation.
Preferably, the strongly basic anion exchanger contains quaternary ammonium salt groups.
Quaternary ammonium salt groups in the strongly basic anion exchanger are easy to ionize, anions in a halogen solution can be stably adsorbed, and compared with a weakly basic anion exchanger containing neutral groups such as tertiary amine and secondary amine, the strongly basic anion exchanger has good stability and is beneficial to selective adsorption of cadmium to a cadmium-containing base metal solution.
Preferably, the mass ratio of the strongly basic anion exchanger and the base metal solution in step (1) is 0.01:100 to 100:0.01, and may be, for example, 0.01:100, 0.1:90, 1:70, 30:1, 70:0.3, 90:0.1 or 100: 0.01.
Preferably, in the case that the base metal solution in step (1) is a zinc solution, the concentration of divalent copper is less than 1 mg/kg.
Preferably, in step (1), the base metal solution is a zinc solution, wherein the concentration of ferric iron is less than 10 mg/kg.
Preferably, when the base metal solution in step (1) is a zinc solution, the concentration of divalent mercury is less than 1 mg/kg.
Preferably, when the base metal solution in the step (1) is a zinc solution and contains bivalent copper higher than 1mg/kg and/or trivalent iron higher than 10mg/kg, the bivalent copper and the trivalent iron can be removed by a precipitation method, an extraction method or an electrolysis method, and then the solution is adsorbed by a strong basic anion exchanger containing chlorine, bromine or iodine; instead of removing the cupric and ferric ions beforehand, a strongly basic anion exchanger containing chlorine and/or bromine can be used for the adsorption.
Preferably, when the base metal solution in the step (1) is a zinc solution and contains more than 1mg/kg of divalent mercury, the divalent mercury is removed by a precipitation method, an extraction method or an electrolysis method, and then the solution is adsorbed by a strong-base anion exchanger containing chlorine, bromine or iodine.
Before the invention utilizes the strong-base anion exchanger containing halogen groups to adsorb zinc base metal solution containing copper, mercury or iron, divalent copper, divalent mercury and trivalent iron in the zinc solution are removed, wherein the presence of the trivalent iron and the divalent copper can oxidize iodide ions into iodine molecules, so that the strong-base anion exchanger loses the adsorption capacity on cadmium; the method improves the adsorption effect of the cadmium by removing the divalent copper, the divalent mercury and the trivalent iron in the zinc solution firstly.
Before the invention utilizes the strong-base anion exchanger containing halogen groups to adsorb the zinc base metal solution containing copper or iron, the invention can select the strong-base anion exchanger containing chlorine or bromine to avoid the oxidation and precipitation reaction without removing divalent copper and trivalent iron in the zinc solution.
Preferably, the adsorption of step (1) comprises a static process or a dynamic process.
The static method of the invention comprises mixing a strongly basic anion exchanger containing halogen groups with a base metal solution containing cadmium, and carrying out standing adsorption.
Preferably, the dynamic process comprises a batch process or a continuous process.
Preferably, the batch process comprises a stirred process.
The stirring method of the present invention includes stirring and mixing a strongly basic anion exchanger containing halogen groups and a base metal solution containing cadmium for adsorption.
Preferably, the continuous process comprises a column-crossing process.
The column passing method comprises the steps of filling a strong-base anion exchanger containing halogen groups into an adsorption column, and allowing a base metal solution containing cadmium to flow through the adsorption column for adsorption.
Preferably, the pH of the first solution is 0.1 to 12, and may be, for example, 0.1, 0.5, 1, 3, 5, 7, 9, 11, or 12.
Preferably, the first solution in step (2) contains chloride ions.
Preferably, the concentration of the chloride ion in the first solution is 0.001mM to 1M, and may be, for example, 0.001mM, 0.01mM, 5mM, 100mM, 300mM, 0.1M, 0.5M or 1M.
Preferably, the first solution includes any one or a combination of at least two of hydrochloric acid solution, lithium chloride aqueous solution, sodium chloride aqueous solution, potassium chloride aqueous solution and ammonium chloride aqueous solution, wherein typical but non-limiting combinations include a combination of hydrochloric acid solution and lithium chloride aqueous solution, a combination of hydrochloric acid solution and sodium chloride aqueous solution, a combination of hydrochloric acid solution and potassium chloride aqueous solution, a combination of hydrochloric acid solution and ammonium chloride aqueous solution, a combination of three of hydrochloric acid solution, lithium chloride aqueous solution and sodium chloride aqueous solution, a combination of three of hydrochloric acid solution, lithium chloride aqueous solution and potassium chloride aqueous solution, a combination of three of hydrochloric acid solution, lithium chloride aqueous solution and ammonium chloride aqueous solution, a combination of three of lithium chloride aqueous solution, sodium chloride aqueous solution and potassium chloride aqueous solution, a combination of three of lithium chloride aqueous solution, sodium chloride aqueous solution and ammonium chloride aqueous solution, a combination of lithium chloride aqueous solution, potassium chloride aqueous solution and ammonium chloride aqueous solution or a combination of sodium chloride aqueous solution, potassium chloride aqueous solution and ammonium chloride aqueous solution.
Preferably, the first solution is eluted at a temperature of 5 to 50 ℃, for example, 5 ℃, 10 ℃, 15 ℃, 20 ℃, 30 ℃, 40 ℃ or 50 ℃.
Preferably, the second solution in step (2) includes any one of deionized water, an aqueous ammonia solution or an aqueous ethylenediamine solution.
The invention adopts deionized water to elute the strongly basic anion exchanger after zinc desorption, so that the adsorption-desorption balance of cadmium can move to the desorption direction; the strong-base anion exchanger after zinc desorption is eluted by ammonia water solution, and because ammonia molecules and cadmium ions can form a cation complex, the desorption of the cadmium ions from the surface of the strong-base anion exchanger is facilitated, and the desorption effect is better than that of deionized water; the strong-base anion exchanger after zinc desorption is eluted by using the ethylenediamine aqueous solution, and the ethylenediamine and cadmium ions can form a high-stability cation complex, so that the desorption of the cadmium ions from the surface of the strong-base anion exchanger is facilitated, and the desorption effect is better than that of deionized water.
Preferably, the concentration of the aqueous ammonia solution is 0.001 mM-10M, and may be, for example, 0.001mM, 0.01mM, 5mM, 1M, 3M, 5M, 8M or 10M.
Preferably, the concentration of the ethylenediamine aqueous solution is 0.001 mM-10M, and may be, for example, 0.001mM, 0.01mM, 5mM, 1M, 3M, 5M, 8M or 10M.
Preferably, the pH of the second solution is 7 to 12, and may be, for example, 7, 8, 9, 10, 11 or 12.
Preferably, the second solution is eluted at a temperature of 5 to 50 ℃, for example, 5 ℃, 10 ℃, 15 ℃, 20 ℃, 30 ℃, 40 ℃ or 50 ℃.
The elution temperature of the second solution is 5-50 ℃, because if the temperature is too low, the aqueous solution is frozen and cannot be eluted; if the temperature is too high, iodide ions are oxidized, ammonia molecules in the ammonia water solution are volatilized, and the elution effect is also influenced.
Preferably, the method further comprises cadmium recovery of the cadmium-containing solution of step (2).
Preferably, the method of cadmium recovery comprises an electrolytic process.
The strongly basic anion exchanger after the cadmium is desorbed, which is obtained in the step (2), is washed by pure water and then returned to the step (1) for reuse.
Preferably, the cadmium-containing base metal solution and the halogen ion-containing solution are mixed to obtain a base metal solution before adsorption, prior to adsorption of the cadmium-containing base metal solution.
In the present invention, it is further preferred to mix the base metal solution with a solution containing halogen ions before adsorbing the base metal solution, wherein the coordination number of cadmium is 4 and 4 halogen atoms can be bonded, and the inventors have found that the strongly basic anion exchanger containing halogen groups can only provide 2 halogen atoms, and the other 2 coordination atoms need to be provided by the solution containing halogen ions, so that the exchange capacity of the resin can be utilized to the maximum extent and the removal rate of cadmium can be improved. When the base metal solution itself contains halogen ions, the solution containing halogen ions may not be added.
Preferably, the molar ratio of the halide ions to the cadmium ions in the base metal solution before adsorption is 2:1 to 1000:1, and may be, for example, 2:1, 10:1, 50:1, 100:1, 500:1, 800:1, or 1000: 1.
Base metals are well known to those skilled in the art as being readily oxidized or corroded, and hydrogen gas, such as manganese, cobalt, copper, iron, nickel, lead, zinc and the like, is typically formed by reacting a base metal with hydrochloric acid. Copper is also considered a base metal which, although not reactive with hydrochloric acid, is relatively easily oxidized.
Preferably, the base metal of the present invention comprises any one or a combination of at least two of manganese, cobalt, nickel, zinc or copper, wherein typical but non-limiting combinations include a combination of manganese and cobalt, a combination of cobalt and nickel, a combination of zinc and copper or a combination of cobalt, nickel or zinc.
The concentration of mM in the solution of the present invention is in the art-recognized concentration units mmol/L, and M is in the art-recognized concentration units mol/L.
As a preferred technical scheme of the invention, the method comprises the following steps:
(1) adsorbing halogen ions in the halogen solution by using the strongly basic anion exchanger to obtain the strongly basic anion exchanger containing halogen groups; mixing a base metal solution containing cadmium and a solution containing halogen ions to obtain a base metal solution before adsorption;
adsorbing the base metal solution before adsorption by using the strongly basic anion exchanger containing halogen groups to obtain a strongly basic anion exchanger after adsorption; wherein the concentration of anions in the halogen solution is 0.001 mM-10M; the pH value of the halogen solution is 0.1-10; the strong-base anion exchanger contains quaternary ammonium salt groups; the mass ratio of the strong-base anion exchanger to the base metal solution is 0.01: 100-100: 0.01; the molar ratio of the halogen ions to the cadmium ions in the base metal solution before adsorption is 2: 1-1000: 1;
(2) when the base metal solution containing cadmium contains zinc, the adsorbed strong-base anion exchanger is eluted by a first solution with the pH of 0.1-12 and the concentration of chloride ions of 0.001 mM-1M at the temperature of 5-50 ℃ to obtain a zinc-containing solution and a zinc-desorbed strong-base anion exchanger; eluting the zinc desorption strong-base anion exchanger by a second solution with the pH value of 7-12 at the temperature of 5-50 ℃ to obtain a cadmium-containing solution;
or when the base metal solution containing cadmium does not contain zinc, eluting the adsorbed strong-base anion exchanger with a second solution with the pH of 7-12 at the temperature of 5-50 ℃ to obtain a cadmium-containing solution;
the second solution comprises any one of deionized water, an ammonia water solution or an ethylene diamine water solution; the concentration of the ammonia water solution is 0.001 mM-10M; the concentration of the ethylenediamine aqueous solution is 0.001 mM-10M; and recovering cadmium from the cadmium-containing solution by adopting an electrolytic method.
Compared with the prior art, the invention has at least the following beneficial effects:
(1) the method for separating and recovering cadmium from the base metal solution provided by the invention selectively adsorbs cadmium in the base metal solution by adopting the strongly basic anion exchanger containing halogen groups, so that the high-efficiency separation of cadmium and other metal elements is realized, the operation is simple, and the treatment cost is low;
(2) the method for separating and recovering cadmium from the base metal solution desorbs the strongly basic anion exchanger after adsorption, recovers cadmium, does not use toxic substances, does not produce environmental pollution, and has good environmental benefit and economic benefit;
(3) the method for separating and recovering cadmium from the base metal solution realizes the high-efficiency recovery of cadmium in the base metal solution, the recovery rate of cadmium is more than or equal to 82.4 percent, and the recovery rate of cadmium is more than or equal to 97.9 percent under better conditions.
Drawings
FIG. 1 is a process flow diagram of a method for separating and recovering cadmium from a base metal solution provided in example 1 of the present invention.
Detailed Description
The present invention is described in further detail below. The following examples are merely illustrative of the present invention and do not represent or limit the scope of the claims, which are defined by the claims.
First, an embodiment
Example 1
The process flow diagram of the method for separating and recovering cadmium from the base metal solution provided by the embodiment is shown in figure 1, and the method comprises the following steps:
(1) adsorbing 1M potassium iodide aqueous solution with the pH value of 7 by using 201 x 7 type strongly basic anion exchange resin containing quaternary ammonium salt groups as halogen solution, washing the strongly basic anion exchange resin with pure water to remove excessive potassium iodide aqueous solution after the strongly basic anion exchange resin reaches adsorption saturation, and obtaining the strongly basic anion exchange resin containing iodide ions; NaOH with the concentration of 0.1M is used for reacting with zinc sulfate containing cadmium, namely base metal solution, so that the concentration of ferric iron in the zinc sulfate solution containing cadmium is reduced to 0.9 mg/kg; extracting the divalent copper with 2-hydroxy-5-nonyl acetoxime with a concentration of 0.1M to reduce the concentration to 0.9 mg/kg; mixing the zinc sulfate solution and the hydrochloric acid solution to obtain a zinc sulfate solution before adsorption; the molar ratio of chloride ions to cadmium ions in the zinc sulfate solution before adsorption is 2: 1;
adsorbing according to the mass ratio of the strongly basic anion exchange resin containing iodine ions to the zinc sulfate solution before adsorption of 1:100 to reach adsorption saturation to obtain adsorbed strongly basic anion exchange resin;
(2) the adsorbed strong-base anion exchange resin is stirred for 1h at 300rpm by a first solution with the chloride ion concentration of 0.05M, namely a hydrochloric acid solution, at the temperature of 20 ℃ for elution, and zinc-desorbed strong-base anion exchange resin and a zinc-containing solution are obtained after filtration;
(3) stirring the zinc desorption strong-base anion exchange resin by a second solution with the pH of 9.2 and the concentration of 0.5M, namely an ethylenediamine aqueous solution at the temperature of 20 ℃ for 1h at 300rpm for elution, and filtering to obtain a cadmium-containing solution; and (3) recovering cadmium from the cadmium-containing solution by adopting an electrolytic method, washing the cadmium with pure water to desorb the strongly basic anion exchange resin, and returning to the step (1) for reuse.
Example 2
The embodiment provides a method for separating and recovering cadmium from a base metal solution, which comprises the following steps:
(1) adsorbing 1M potassium iodide aqueous solution with the pH value of 7 by using Amberlite IRA 900 type strongly basic anion exchange resin containing quaternary ammonium salt groups, washing the strongly basic anion exchange resin with pure water to remove excessive potassium iodide aqueous solution after the strongly basic anion exchange resin is saturated by adsorption, and obtaining the strongly basic anion exchange resin containing iodide ions;
reacting NaOH with the concentration of 0.1M with zinc chloride containing cadmium to reduce the concentration of ferric iron in the zinc chloride solution to 0.8mg/kg, and extracting divalent copper with 2-hydroxy-5-nonyl acetoxime with the concentration of 0.1M to reduce the concentration of the divalent copper to 0.7 mg/kg; adsorbing according to the mass ratio of the strongly basic anion exchange resin containing iodine ions to the zinc chloride solution of 1:100 to reach adsorption saturation to obtain adsorbed strongly basic anion exchange resin;
(2) stirring the adsorbed strong-base anion exchange resin by hydrochloric acid solution with the chloride ion concentration of 0.1mM for 1h at the temperature of 25 ℃ at 1000rpm for elution, and filtering to obtain zinc-desorbed strong-base anion exchange resin;
(3) the zinc desorption strong-base anion exchange resin is eluted by ethylenediamine aqueous solution with the pH of 9.2 and the concentration of 0.5M for 1 hour at the temperature of 25 ℃ by stirring at 1000rpm, and the cadmium-containing solution is obtained after filtration; and (3) recovering cadmium from the cadmium-containing solution by adopting an electrolytic method, washing the strongly basic anion exchange resin with the cadmium for desorbing iodine-containing ions by using pure water, and returning to the step (1) for reuse.
Example 3
The embodiment provides a method for separating and recovering cadmium from a base metal solution, which comprises the following steps:
(1) adsorbing 1M potassium bromide aqueous solution with the pH value of 7 by using ZB-2 type strongly basic anion exchange fiber containing quaternary ammonium salt groups, washing the strongly basic anion exchange fiber by using pure water to remove excessive potassium bromide aqueous solution after the strongly basic anion exchange fiber is saturated in adsorption, and obtaining the strongly basic anion exchange fiber containing bromide ions;
mixing copper sulfate solution containing cadmium with hydrobromic acid solution with the concentration of 1M to obtain copper sulfate solution before adsorption; the molar ratio of bromide ions to cadmium ions in the copper sulfate solution before adsorption is 2: 1; the concentration of ferric iron in the copper sulfate solution is 0.6 mg/kg;
adsorbing according to the mass ratio of the strong-base anion exchange fiber containing bromide ions to the copper sulfate solution before adsorption of 1:500 to reach adsorption saturation, and obtaining the strong-base anion exchange fiber after adsorption;
(2) stirring the adsorbed strongly basic anion exchange fiber by using an ethylenediamine aqueous solution with the pH of 9.5 and the concentration of 1M at 25 ℃ for 1h at 1000rpm for elution, and filtering to obtain a cadmium-containing solution; and (3) recovering cadmium from the cadmium-containing solution by adopting an electrolytic method, washing the cadmium with pure water to desorb the strongly basic anion exchange fiber, and returning to the step (1) for reuse.
Example 4
The embodiment provides a method for separating and recovering cadmium from a base metal solution, which comprises the following steps:
(1) adsorbing 1M potassium iodide aqueous solution with the pH value of 0.5 by using D201 type strongly basic anion exchange resin containing quaternary ammonium salt groups, washing the strongly basic anion exchange resin with pure water to remove excessive potassium iodide aqueous solution after the strongly basic anion exchange resin reaches adsorption saturation, and obtaining the strongly basic anion exchange resin containing iodide ions;
mixing a nickel nitrate solution containing cadmium and a hydrobromic acid solution with the concentration of 0.1M to obtain a nickel nitrate solution before adsorption;
the molar ratio of bromide ions to cadmium ions in the nickel nitrate solution before adsorption is 2: 1; adsorbing according to the mass ratio of the strongly basic anion exchange resin containing iodine ions to the nickel nitrate solution containing cadmium of 1:100 to reach adsorption saturation to obtain adsorbed strongly basic anion exchange resin;
(2) the zinc desorption strong-base anion exchange resin is eluted by stirring an ethylenediamine aqueous solution with the pH of 9.0 and the concentration of 0.1M for 1h at the temperature of 40 ℃ at the speed of 600rpm, and a cadmium-containing solution is obtained after filtration; and (3) recovering cadmium from the cadmium-containing solution by adopting an electrolytic method, washing the cadmium with pure water to desorb the strongly basic anion exchange resin, and returning to the step (1) for reuse.
Example 5
The embodiment provides a method for separating and recovering cadmium from a base metal solution, which comprises the following steps:
(1) filling 10g D201 strong-base ion exchange resin into a glass tube with an inner diameter of 15mm and a bottom filled with glass fiber to prepare an ion exchange column (adsorption column), enabling 100mL of 1M potassium iodide aqueous solution with the pH of 8 to flow through the adsorption column at a flow rate of 1mL/min for adsorption, enabling the strong-base anion exchange resin to reach adsorption saturation, and enabling pure water to flow through the strong-base anion exchange resin at a flow rate of 1mL/min to remove excessive potassium iodide aqueous solution to obtain the iodine ion-containing strong-base anion exchange resin;
the concentration of ferric iron and the concentration of cupric copper in the zinc sulfate solution containing cadmium are respectively 0.5mg/kg and 0.9 mg/kg; mixing the zinc sulfate solution containing cadmium and the hydrobromic acid solution to obtain a zinc sulfate solution before adsorption; the molar ratio of bromide ions to cadmium ions in the zinc sulfate solution before adsorption is 2: 1;
enabling the zinc sulfate solution to flow through the strong-base anion exchange resin at the flow rate of 1mL/min for adsorption according to the mass ratio of the strong-base anion exchange resin containing bromide ions to the zinc sulfate solution before adsorption of 1:100 to obtain the adsorbed strong-base anion exchange resin;
(2)30mL of hydrochloric acid solution with the chloride ion concentration of 0.1M flows through the adsorbed strongly basic anion exchange resin at the flow rate of 1mL/min at the temperature of 25 ℃ for elution to obtain zinc-desorbed strongly basic anion exchange resin;
(3) under the condition of 30 ℃, ammonia water solution with pH of 11.5 and concentration of 0.5M flows through the zinc desorption strong base anion exchange resin at the flow rate of 1mL/min for elution to obtain cadmium-containing solution; and (3) recovering cadmium from the cadmium-containing solution by adopting an electrolytic method, washing the cadmium with pure water to desorb the strong-base anion exchange resin containing bromide ions, and returning to the step (1) for reuse.
Example 6
This example provides a method for separating and recovering cadmium from a base metal solution, which is the same as example 1 except that a zinc sulfate solution and a hydrochloric acid solution are not mixed in step (1).
Example 7
This example provides a method for separating and recovering cadmium from a base metal solution, which is the same as that of example 1 except that in step (1), basic anion exchange fibers containing quaternary ammonium groups of type ZB-2 were used in place of a strong basic anion exchange resin containing quaternary ammonium groups of type 201X 7.
Example 8
This example provides a process for the separation and recovery of cadmium from a base metal solution which is the same as example 1 except that deionized water is used to elute the zinc desorption strongly basic anion exchange resin in step (3).
Example 9
This example provides a method for separating and recovering cadmium from a base metal solution, which is the same as example 1 except that in step (1), a chlorine type 201 x 7 type strongly basic anion exchange resin containing quaternary ammonium salt groups is directly used for adsorption with a zinc sulfate solution before adsorption.
Third, test and results
The cadmium content in the cadmium-containing base metal solution and the cadmium-containing solution obtained by elution are measured by adopting an atomic absorption photometry method or an inductively coupled plasma spectrometry method, the cadmium recovery rate is calculated by a standard curve method, and the results of examples 1-9 and comparative example 1 are shown in table 1.
TABLE 1
| Cadmium recovery rate | |
| Example 1 | 95.6％ |
| Example 2 | 95.7％ |
| Example 3 | 94.9％ |
| Example 4 | 95.2％ |
| Example 5 | 92.3％ |
| Example 6 | 82.4％ |
| Example 7 | 97.9％ |
| Example 8 | 73.8％ |
| Example 9 | 74.2％ |
From table 1, the following points can be seen: (1) it can be seen from the comprehensive examples 1 to 9 that the method for separating and recovering cadmium from the base metal solution provided by the invention can realize the efficient separation of cadmium and other metal elements in the base metal solution, the recovery rate of cadmium is more than or equal to 73.8%, and under better conditions, the recovery rate of cadmium is more than or equal to 97.9%;
(2) combining example 1 with example 6, it can be seen that the zinc sulfate solution and hydrochloric acid solution were mixed in step (1) of example 1, and the cadmium recovery rate was high and 95.6% in example 1, and the cadmium recovery rate was reduced to 82.4% in example 6, compared to the case where the zinc sulfate solution and hydrochloric acid solution were not mixed in step (1) of example 6; therefore, before the base metal solution is adsorbed, the base metal solution and the solution containing the halogen ions are preferably mixed, so that the cadmium removal rate is improved;
(3) combining example 1 with example 7, it can be seen that example 1 using a 201 × 7 type of strong base anion exchange resin containing quaternary ammonium salt groups, compared to example 7 using a ZB-2 type of basic anion exchange fiber containing quaternary ammonium groups, the cadmium recovery rate in example 1 was 95.6%, and the cadmium recovery rate in example 7 was 97.9%, mainly because the quaternary ammonium salt groups on the surface of the strong base fibers did not require an intra-particle diffusion process, and the mass transfer rate was fast; therefore, under the same operation condition, the strongly basic anion exchange fiber containing quaternary ammonium salt groups is further preferred, so that the removal rate of cadmium in the base metal solution can be obviously improved;
(4) it can be seen from the combination of example 1 and example 8 that, in the step (3) of example 1, the zinc desorption strong base anion exchange resin is eluted by the ethylenediamine aqueous solution, and compared with the step (3) of example 8, the zinc desorption strong base anion exchange resin is eluted by deionized water, the cadmium recovery rate of example 1 is significantly higher than that of example 8; therefore, the method adopts the specific solution to elute the zinc desorption strong-base anion exchange resin, and can obviously improve the desorption rate of cadmium in the adsorbed strong-base anion exchange agent;
(5) combining example 1 and example 9, it can be seen that, in step (1) of example 1, after saturated adsorption of the aqueous solution of potassium iodide with the 201 × 7 type strongly basic anion exchange resin containing quaternary ammonium salt groups, adsorption with the zinc sulfate solution before adsorption is performed, compared to the case of example 9, in step (1), in which the chloride type 201 × 7 type strongly basic anion exchange resin containing quaternary ammonium salt groups is directly used for adsorption with the zinc sulfate solution before adsorption, the cadmium recovery rate in example 1 is significantly higher than that in example 9; therefore, the invention preferably selects the strongly basic anion exchanger containing iodine ions to adsorb the base metal solution containing cadmium, and can obviously improve the removal rate of cadmium in the base metal solution.
In conclusion, the method for separating and recovering cadmium from the base metal solution provided by the invention realizes the high-efficiency separation of cadmium and other metal elements, is simple to operate, has low treatment cost, does not use toxic substances, does not produce environmental pollution, and has good environmental benefit and economic benefit.
The applicant declares that the present invention illustrates the detailed structural features of the present invention through the above embodiments, but the present invention is not limited to the above detailed structural features, that is, it does not mean that the present invention must be implemented depending on the above detailed structural features. It should be understood by those skilled in the art that any modifications of the present invention, equivalent substitutions of selected components of the present invention, additions of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (10)
1. A method for separating and recovering cadmium from a base metal solution is characterized by comprising the following steps:
(1) adsorbing a base metal solution containing cadmium by using a strongly basic anion exchanger containing halogen groups to obtain an adsorbed strongly basic anion exchanger;
(2) when the base metal solution containing cadmium contains zinc, eluting the adsorbed strong-base anion exchanger by using a first solution to obtain a zinc-containing solution and a zinc-desorbed strong-base anion exchanger; eluting the zinc desorption strong-base anion exchanger by using a second solution to obtain a cadmium-containing solution;
or when the base metal solution containing cadmium does not contain zinc, eluting the adsorbed strong-base anion exchanger by a second solution to obtain the solution containing cadmium.
2. The method according to claim 1, wherein the preparation method of the halogen group-containing strongly basic anion exchanger of step (1) comprises: adsorbing halogen ions in the halogen solution by using the strongly basic anion exchanger to obtain the strongly basic anion exchanger containing halogen groups;
preferably, the anion in the halogen solution comprises any one of chloride, bromide or iodide or a combination of at least two thereof;
preferably, the concentration of the anion in the halogen solution is 0.001 mM-10M;
preferably, the pH of the halogen solution is 0.1-10.
3. The method of claim 2, wherein the strongly basic anion exchanger of step (1) comprises any one of a strongly basic anion exchange resin, a strongly basic anion exchange fiber, or a strongly basic anion exchange membrane;
preferably, the strongly basic anion exchanger contains quaternary ammonium salt groups.
4. A process according to any one of claims 1 to 3, wherein the mass ratio of the strongly basic anion exchanger of step (1) to the base metal solution is from 0.01:100 to 100: 0.01.
5. The method according to any one of claims 1 to 4, wherein the pH of the first solution in the step (2) is 0.1 to 12.
6. The method according to any one of claims 1 to 5, wherein the first solution in step (2) contains chloride ions;
preferably, the concentration of the chloride ions in the first solution is 0.001 mM-1M;
preferably, the first solution comprises any one of hydrochloric acid solution, lithium chloride aqueous solution, sodium chloride aqueous solution, potassium chloride aqueous solution and ammonium chloride aqueous solution or the combination of at least two of the hydrochloric acid solution, the lithium chloride aqueous solution, the sodium chloride aqueous solution, the potassium chloride aqueous solution and the ammonium chloride aqueous solution;
preferably, the elution temperature of the first solution is 5-50 ℃.
7. The method according to any one of claims 1 to 6, wherein the second solution in the step (2) comprises any one of deionized water, an aqueous ammonia solution or an aqueous ethylenediamine solution;
preferably, the concentration of the ammonia water solution is 0.001 mM-10M;
preferably, the concentration of the ethylenediamine aqueous solution is 0.001 mM-10M;
preferably, the pH of the second solution is 7-12;
preferably, the temperature of the second solution for elution is 5-50 ℃.
8. The method according to any one of claims 1 to 7, further comprising performing cadmium recovery on the cadmium-containing solution of step (2);
preferably, the method of cadmium recovery comprises an electrolytic process.
9. A method according to any one of claims 1 to 8, wherein the base metal solution and the solution containing halogen ions are mixed prior to adsorption of the base metal solution to produce a pre-adsorption base metal solution;
preferably, the molar ratio of the halogen ions to the cadmium ions in the base metal solution before adsorption is 2: 1-1000: 1.
10. A method according to any one of claims 1 to 9, characterized in that the method comprises the steps of:
(1) the strongly basic anion exchanger adsorbs halogen ions in the halogen solution in a saturated way to obtain the strongly basic anion exchanger containing halogen groups; mixing a base metal solution containing cadmium and a solution containing halogen ions to obtain a base metal solution before adsorption;
adsorbing the base metal solution before adsorption by using the strongly basic anion exchanger containing halogen groups to obtain a strongly basic anion exchanger after adsorption; wherein the concentration of anions in the halogen solution is 0.001 mM-10M; the pH value of the halogen solution is 0.1-10; the strong-base anion exchanger contains quaternary ammonium salt groups; the mass ratio of the strong-base anion exchanger to the base metal solution is 0.01: 100-100: 0.01; the molar ratio of the halogen ions to the cadmium ions in the base metal solution before adsorption is 2: 1-1000: 1;
(2) when the base metal solution containing cadmium contains zinc, the adsorbed strong-base anion exchanger is eluted by a first solution with the pH of 0.1-12 and the concentration of chloride ions of 0.001 mM-1M at the temperature of 5-50 ℃ to obtain a zinc-containing solution and a zinc-desorbed strong-base anion exchanger; eluting the zinc desorption strong-base anion exchanger by a second solution with the pH value of 7-12 at the temperature of 5-50 ℃ to obtain a cadmium-containing solution;
or when the base metal solution containing cadmium does not contain zinc, eluting the adsorbed strong-base anion exchanger with a second solution with the pH of 7-12 at the temperature of 5-50 ℃ to obtain a cadmium-containing solution;
the second solution comprises any one of deionized water, an ammonia water solution or an ethylene diamine water solution; the concentration of the ammonia water solution is 0.001 mM-10M; the concentration of the ethylenediamine aqueous solution is 0.001 mM-10M; and recovering cadmium from the cadmium-containing solution by adopting an electrolytic method.
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