CN107779603B - Method for preparing lead carbonate from lead oxide waste - Google Patents
Method for preparing lead carbonate from lead oxide waste Download PDFInfo
- Publication number
- CN107779603B CN107779603B CN201610758033.1A CN201610758033A CN107779603B CN 107779603 B CN107779603 B CN 107779603B CN 201610758033 A CN201610758033 A CN 201610758033A CN 107779603 B CN107779603 B CN 107779603B
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- Prior art keywords
- lead
- carbonate
- sulfate
- solution
- waste
- 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 - Fee Related
Links
- 238000000034 method Methods 0.000 title claims abstract description 83
- 239000002699 waste material Substances 0.000 title claims abstract description 80
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 229910000464 lead oxide Inorganic materials 0.000 title claims abstract description 68
- MFEVGQHCNVXMER-UHFFFAOYSA-L 1,3,2$l^{2}-dioxaplumbetan-4-one Chemical compound [Pb+2].[O-]C([O-])=O MFEVGQHCNVXMER-UHFFFAOYSA-L 0.000 title claims abstract description 53
- 229910000003 Lead carbonate Inorganic materials 0.000 title claims abstract description 53
- PIJPYDMVFNTHIP-UHFFFAOYSA-L lead sulfate Chemical compound [PbH4+2].[O-]S([O-])(=O)=O PIJPYDMVFNTHIP-UHFFFAOYSA-L 0.000 claims abstract description 77
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 65
- 230000008569 process Effects 0.000 claims abstract description 38
- 239000000706 filtrate Substances 0.000 claims abstract description 34
- 239000012535 impurity Substances 0.000 claims abstract description 25
- 239000002131 composite material Substances 0.000 claims abstract description 24
- 239000012043 crude product Substances 0.000 claims abstract description 23
- 239000000126 substance Substances 0.000 claims abstract description 22
- 239000000047 product Substances 0.000 claims abstract description 16
- 238000001914 filtration Methods 0.000 claims abstract description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 88
- 239000000243 solution Substances 0.000 claims description 78
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 42
- 238000003756 stirring Methods 0.000 claims description 28
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical group O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 24
- 238000003763 carbonization Methods 0.000 claims description 23
- 238000002386 leaching Methods 0.000 claims description 23
- 238000004073 vulcanization Methods 0.000 claims description 21
- 239000007788 liquid Substances 0.000 claims description 19
- 239000011505 plaster Substances 0.000 claims description 18
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 15
- 235000011054 acetic acid Nutrition 0.000 claims description 13
- 238000000926 separation method Methods 0.000 claims description 13
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 12
- 239000001569 carbon dioxide Substances 0.000 claims description 12
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 12
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 10
- 239000001099 ammonium carbonate Substances 0.000 claims description 10
- 239000013078 crystal Substances 0.000 claims description 10
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 9
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 8
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 8
- 229910052802 copper Inorganic materials 0.000 claims description 8
- 239000010949 copper Substances 0.000 claims description 8
- 229910052725 zinc Inorganic materials 0.000 claims description 8
- 239000011701 zinc Substances 0.000 claims description 8
- KEQXNNJHMWSZHK-UHFFFAOYSA-L 1,3,2,4$l^{2}-dioxathiaplumbetane 2,2-dioxide Chemical compound [Pb+2].[O-]S([O-])(=O)=O KEQXNNJHMWSZHK-UHFFFAOYSA-L 0.000 claims description 7
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 7
- 239000002893 slag Substances 0.000 claims description 7
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 6
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 6
- 238000004064 recycling Methods 0.000 claims description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 6
- 235000017550 sodium carbonate Nutrition 0.000 claims description 6
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 5
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000011707 mineral Substances 0.000 claims description 5
- 235000010755 mineral Nutrition 0.000 claims description 5
- 235000006408 oxalic acid Nutrition 0.000 claims description 5
- 230000020477 pH reduction Effects 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- 239000004071 soot Substances 0.000 claims description 5
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 4
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 4
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 4
- 235000015165 citric acid Nutrition 0.000 claims description 4
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 4
- 239000010908 plant waste Substances 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 3
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 3
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 3
- BIGPRXCJEDHCLP-UHFFFAOYSA-N ammonium bisulfate Chemical compound [NH4+].OS([O-])(=O)=O BIGPRXCJEDHCLP-UHFFFAOYSA-N 0.000 claims description 3
- 235000019253 formic acid Nutrition 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000011975 tartaric acid Substances 0.000 claims description 3
- 235000002906 tartaric acid Nutrition 0.000 claims description 3
- QWSOGKQKELMGCQ-UHFFFAOYSA-N 1-azaniumylpropan-2-ylazanium;diacetate Chemical compound CC(O)=O.CC(O)=O.CC(N)CN QWSOGKQKELMGCQ-UHFFFAOYSA-N 0.000 claims description 2
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 2
- 239000004254 Ammonium phosphate Substances 0.000 claims description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 235000019270 ammonium chloride Nutrition 0.000 claims description 2
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 2
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 2
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 2
- 150000003863 ammonium salts Chemical group 0.000 claims description 2
- 239000004202 carbamide Substances 0.000 claims description 2
- 238000010000 carbonizing Methods 0.000 claims description 2
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 2
- IFQUWYZCAGRUJN-UHFFFAOYSA-N ethylenediaminediacetic acid Chemical compound OC(=O)CNCCNCC(O)=O IFQUWYZCAGRUJN-UHFFFAOYSA-N 0.000 claims description 2
- 239000010881 fly ash Substances 0.000 claims description 2
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 2
- 239000011736 potassium bicarbonate Substances 0.000 claims description 2
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 2
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 235000011181 potassium carbonates Nutrition 0.000 claims description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 2
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims 1
- 239000002253 acid Substances 0.000 abstract description 19
- 238000011084 recovery Methods 0.000 abstract description 18
- 239000012452 mother liquor Substances 0.000 abstract description 12
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 238000003723 Smelting Methods 0.000 abstract description 3
- 125000004122 cyclic group Chemical group 0.000 abstract 1
- 229910052924 anglesite Inorganic materials 0.000 description 22
- 238000006477 desulfuration reaction Methods 0.000 description 18
- 230000023556 desulfurization Effects 0.000 description 18
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 10
- 235000011114 ammonium hydroxide Nutrition 0.000 description 10
- 239000002244 precipitate Substances 0.000 description 10
- 239000002994 raw material Substances 0.000 description 10
- 238000002425 crystallisation Methods 0.000 description 9
- 230000008025 crystallization Effects 0.000 description 9
- HTUMBQDCCIXGCV-UHFFFAOYSA-N lead oxide Chemical compound [O-2].[Pb+2] HTUMBQDCCIXGCV-UHFFFAOYSA-N 0.000 description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 238000003860 storage Methods 0.000 description 6
- ZXSQEZNORDWBGZ-UHFFFAOYSA-N 1,3-dihydropyrrolo[2,3-b]pyridin-2-one Chemical compound C1=CN=C2NC(=O)CC2=C1 ZXSQEZNORDWBGZ-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 239000008139 complexing agent Substances 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- LKZMBDSASOBTPN-UHFFFAOYSA-L silver carbonate Substances [Ag].[O-]C([O-])=O LKZMBDSASOBTPN-UHFFFAOYSA-L 0.000 description 4
- 229910001958 silver carbonate Inorganic materials 0.000 description 4
- 239000008247 solid mixture Substances 0.000 description 4
- 238000004448 titration Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 3
- 230000003009 desulfurizing effect Effects 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 3
- 238000005486 sulfidation Methods 0.000 description 3
- 230000001502 supplementing effect Effects 0.000 description 3
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- HOQPTLCRWVZIQZ-UHFFFAOYSA-H bis[[2-(5-hydroxy-4,7-dioxo-1,3,2$l^{2}-dioxaplumbepan-5-yl)acetyl]oxy]lead Chemical compound [Pb+2].[Pb+2].[Pb+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HOQPTLCRWVZIQZ-UHFFFAOYSA-H 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 229910052793 cadmium Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 230000000536 complexating effect Effects 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- YADSGOSSYOOKMP-UHFFFAOYSA-N lead dioxide Inorganic materials O=[Pb]=O YADSGOSSYOOKMP-UHFFFAOYSA-N 0.000 description 2
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000005987 sulfurization reaction Methods 0.000 description 2
- 239000010926 waste battery Substances 0.000 description 2
- -1 1-fluoroacetic acid Chemical compound 0.000 description 1
- 239000005635 Caprylic acid (CAS 124-07-2) Substances 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical compound NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- NZNMSOFKMUBTKW-UHFFFAOYSA-N cyclohexanecarboxylic acid Chemical compound OC(=O)C1CCCCC1 NZNMSOFKMUBTKW-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
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- 238000002474 experimental method Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000003500 flue dust Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229940046892 lead acetate Drugs 0.000 description 1
- 150000002611 lead compounds Chemical class 0.000 description 1
- JQJCSZOEVBFDKO-UHFFFAOYSA-N lead zinc Chemical compound [Zn].[Pb] JQJCSZOEVBFDKO-UHFFFAOYSA-N 0.000 description 1
- HWSZZLVAJGOAAY-UHFFFAOYSA-L lead(II) chloride Chemical compound Cl[Pb]Cl HWSZZLVAJGOAAY-UHFFFAOYSA-L 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229960002446 octanoic acid Drugs 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
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- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
Images
Classifications
-
- 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
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
- C22B7/007—Wet processes by acid leaching
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G21/00—Compounds of lead
- C01G21/14—Carbonates
-
- 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
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/02—Roasting processes
-
- 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
- C22B13/00—Obtaining lead
- C22B13/04—Obtaining lead by wet processes
- C22B13/045—Recovery from waste materials
-
- 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)
- Mechanical Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Geochemistry & Mineralogy (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
A method for preparing lead carbonate from lead oxide waste, belonging to the field of recovery of lead oxide-containing waste. The method comprises the following steps: (1) and converting the lead oxide waste into a crude lead sulfate product by using a sulfuric acid composite solution. (2) Dissolving the crude lead sulfate product in the step (1) by using an X-Y conjugated solution to dissolve lead sulfate in the crude product, and filtering to obtain lead sulfate filtrate and insoluble impurities. (3) And (3) adding a carbon-containing substance into the lead sulfate filtrate obtained in the step (2), and separating to obtain the lead carbonate. The method can be widely applied to waste lead-acid battery lead paste from various sources, waste materials generated in the production of lead-acid batteries and lead-containing waste materials generated in the smelting process, and has the advantages of high lead recovery rate, cyclic utilization of mother liquor and the like.
Description
Technical Field
The invention relates to a method for recovering lead oxide waste and preparing lead carbonate, belonging to the field of recovery of lead oxide-containing waste.
Background
In recent years, with the progress of industrialization and urbanization in China, the lead industry in China develops rapidly and gradually occupies an important position in the global lead industry chain. China is the first lead producing country in the world over the United states in 2003, and the yield of the lead is reduced year by year in the counter western countries due to the environmental pollution problem in the process of producing the lead. In 2004, China is the first lead consuming nation in the world beyond the United states. According to data published by the international lead-zinc research group, the global lead output is 1037.2 ten thousand tons in 2011, and the consumption is 1021.6 ten thousand tons; the refined lead yield of China is 464.8 ten thousand tons, the consumption is 463.2 ten thousand tons, and the refined lead yield and the consumption of China approximately account for 45 percent of the global market. The main consumer areas for lead are batteries, cable sheathing, lead oxide and lead. Lead-acid batteries are widely used due to their advantages of low price, high safety, mature technology, etc. The storage battery industry is the main field of lead consumption, and accounts for about 80% of the total consumption.
The large volume of lead production and lead consumption is accompanied by lead recovery, and lead oxide waste from lead production to lead consumption is: the method comprises the following steps of disassembling lead plaster, waste grids, flue ash, waste lead plaster in the battery preparation process, lithopone leaching residues, lead anode mud, copper converter soot slag, mineral dressing tailings, zinc factory waste residues and the like. Aiming at the different lead oxide wastes, the pyrometallurgical recovery technology is adopted internationally. However, secondary pollution problem exists in pyrometallurgical smelting, and scholars at home and abroad are actively researching wet lead regeneration technology aiming at the secondary pollution problem of pyrometallurgical smelting
The wet treatment fundamentally eliminates lead dust and SO2The secondary pollution problem of pollution is an environment-friendly lead oxide waste treatment method. The final product of wet recovery of lead can be a lead compound or metallic lead. Basically adopts the technical process of leaching by using a leaching agent, and purifying, crystallizing or precipitating the leaching solution to produce lead salt or electrolytically produce metallic lead. Waste lead-acid storage battery waste lead paste is converted to obtain lead oxide powder, wherein the published patent CN201210121636.2 of Huazhong university of science and technology utilizes raw materials such as sodium carbonate and the like to perform desulfurization reaction with the waste lead paste, then utilizes the desulfurization lead paste to react with citric acid solution and dry to obtain lead citrate, and the lead citrate is roasted to finally obtain superfine lead oxide powder. Although the method accords with the characteristics of clean production, the high-purity lead oxide powder cannot be prepared because the whole step has no impurity removal link and the additive added in the preparation process of the lead-acid battery cannot be removed. The method is strict in raw material selection, only suitable for recovering waste lead plaster, and not suitable for other lead oxide wastes (lithopone leaching slag, lead anode mud, copper converter soot slag, mineral dressing tailings, zinc plant waste residues and the like). A method for desulfurizing lead plaster of waste lead-acid storage batteries is disclosed, wherein a Wuhan university of science and technology publication patent CN102925698B utilizes ammonia water or a solution containing amino substances to dissolve the lead plaster, but the single ammonia water or the solution containing the amino substances has lower dissolving capacity for lead sulfate in the lead plaster, so that the ammonia water or the solution containing the amino substances is wasted, and the production efficiency is lower. Secondly, the process is more demanding with respect to the source of the raw material, sinceThe ammonia water has a relatively strong complexing ability with respect to metal oxides such as Zn, Cu, etc., and the method cannot effectively remove impurities when the raw materials contain the above metal oxides.
A method for desulfurizing lead plaster of waste lead-acid storage batteries is characterized in that a south China university published patent CN 103633394A utilizes carbonate to desulfurize the lead plaster of the waste lead-acid storage batteries, and the whole system is a solid-liquid reaction, solid-phase lead sulfate reacts with a carbonate solution, and the generated lead carbonate is a precipitate which is more insoluble than the lead sulfate, so that the precipitate which is coated outside the lead carbonate and is internally provided with a lead sulfate core is easily formed, the problem of lead sulfate residue exists, the desulfurization rate is low, and the purity of the product lead carbonate is low.
A method for preparing a mixture of lead carbonate and silver carbonate by using filter residue obtained in the production of lithopone is disclosed in patent CN 102167393A, wherein lead chloride and silver chloride in raw materials react with sodium carbonate to generate the lead carbonate, the silver carbonate and sodium chloride, an elemental sulfur filter cake and a fine emulsion are separated by coarse filtration, and a mixture filter cake of the lead carbonate and the silver carbonate and a sodium chloride filtrate are separated by fine filtration of the fine emulsion. Because the method does not separately recover Pb element and Ag element, the prepared product is a mixture of lead carbonate and silver carbonate, and the economic value is not high. And other insoluble impurities in the product cannot be effectively removed only by simple coarse filtration and fine filtration.
In the invention patent (CN105197988A), a lead sulfate (PbSO) is disclosed4) The invention adopts PbSO to separate and refine4Crude product is used as raw material, and comparatively single NH is used3·H2O-(NH4)2SO4The aqueous solution is used as a solvent, and the steps of leaching dissolution, impurity removal and refining, evaporative crystallization, solid-liquid separation and the like are adopted to realize PbSO4The separation and purification of (1). The main problem of the invention is to dissolve PbSO by using 36mol/L ultrahigh pressure ammonia water under 30-100 atmospheric pressures of lead sulfate4The ammonia water is far beyond the operable condition of 6-12mol/L of normal-pressure ammonia water, and the high-pressure and high-concentration ammonia water has great harm to the design of a reaction kettle and the health of staff. It can be seen that a single aqueous ammonia solution has difficulty in dissolving lead sulfate.
For most of the current processes for recovering lead oxide waste to produce lead carbonate, the sulfidation process of lead-containing waste and the subsequent desulfurization process of lead sulfate are indispensable reaction steps. From the above prior art, there are the following major problems:
(1) lead oxide is inefficient in the sulfidation process and is easily covered by low solubility lead sulfate, resulting in difficult sulfidation of the raw material core.
(2) In the process of desulfurizing lead sulfate, incomplete sulfuration is also caused by the difficult dissolution of lead sulfate and lead carbonate.
(3) There is no effective impurity removal link in the sulfuration and carbonization processes, resulting in that the prepared lead carbonate is mixed with a large amount of various impurities in the original lead oxide waste. Therefore, in the process of wet-process lead oxide waste recovery, the invention of a novel lead oxide-containing waste material directly recovered into high-purity lead carbonate is needed to be invented, and the problem to be solved in the current wet-process lead recovery is needed to be solved.
Disclosure of Invention
The invention aims to overcome the technical defects in the prior art, and provides a method for preparing lead carbonate from lead oxide waste aiming at the problems of high recovery cost of the lead oxide waste, low economic value of byproducts, low purity of produced products and the like.
In order to achieve the purpose, the technical scheme adopted by the invention comprises three steps of (1) vulcanization, (2) leaching and (3) carbonization. The method comprises the steps of (1) promoting lead oxide waste materials to be converted into lead sulfate through a vulcanization process, (2) dissolving generated lead sulfate through a conjugated complexing agent to separate a lead sulfate solution from impurities, (3) finally obtaining high-purity lead carbonate through a carbonization process of the lead sulfate solution, and recycling the conjugated complexing agent.
The technical scheme adopted by the invention comprises the following specific steps:
(1) and (3) vulcanization: acidifying the lead oxide waste material by using a sulfuric acid composite solution A to obtain a lead sulfate crude product; the sulfuric acid composite solution A is a mixed solution of sulfuric acid and other inorganic acids or sulfuric acid and organic acids;
(2) leaching: dissolving and filtering a lead sulfate crude product obtained by acidification of a sulfuric acid composite solution A by using an X-Y conjugated solution to obtain a lead sulfate filtrate and insoluble impurities; x in the X-Y conjugated solution is one or more of organic amine or ammonia, and Y is ammonium salt;
(3) carbonizing: and (3) carrying out contact reaction on the lead sulfate filtrate obtained in the step (2) and a carbon-containing substance to obtain lead carbonate and filtrate B, wherein the lead carbonate is carbon dioxide, carbonate or an organic substance capable of decomposing carbon dioxide.
In the step (1) of the method for preparing lead carbonate from lead oxide waste, the other inorganic acid in the sulfuric acid composite solution A is preferably one or two of nitric acid, phosphoric acid, hydrochloric acid and perchloric acid, and the organic acid is preferably one or two of formic acid, acetic acid, propionic acid, butyric acid, caprylic acid, adipic acid, oxalic acid, malonic acid, tartaric acid, citric acid, methanesulfonic acid, α aminocarboxylic acid, 1-fluoroacetic acid, sulfamic acid and cyclohexanoic acid.
Before the step (1) of the present invention is carried out, the lead oxide waste material can be converted into lead oxide waste material with relatively higher content by pre-conversion treatment, such as pre-roasting in air atmosphere to remove Pb and PbO in the raw material2And (5) obtaining the roasted lead paste.
In the step (1) of the method for preparing lead carbonate from lead oxide waste, the lead oxide waste is added into a reaction kettle, a sulfuric acid composite solution A is added into the reaction kettle, the reaction temperature is controlled at 20-120 ℃, and solid-liquid separation is carried out after continuous stirring for 0.1-5h, so as to obtain a crude product of lead sulfate after acidification and conversion and a filtrate.
Preferably, the reaction temperature is 20 to 100 deg.C, more preferably 20 to 80 deg.C. The acidification time is based on the fact that complete vulcanization can be achieved.
In the step (2) of the method for preparing lead carbonate from lead oxide waste, the sulfurized crude lead sulfate needs to be added into a reaction kettle, and sufficient X-Y conjugated solution is added into the reaction kettle; the X-Y conjugated solution is prepared by the following steps, wherein X is preferably one or two of ammonia, ethylenediamine, propylenediamine, ethylenediamine diacetic acid, ethylenediamine tetraacetic acid, propylenediamine diacetic acid, diethanolamine and triethanolamine; y is preferably one or two of ammonium chloride, ammonium bisulfate, ammonium sulfate, ammonium nitrate, ammonium carbonate, ammonium bicarbonate, ammonium monohydrogen phosphate, ammonium dihydrogen phosphate and ammonium phosphate. In order to better realize the leaching effect of the lead sulfate, the concentration of X in the conjugate solution is controlled to be 2-15mol/L, the concentration of Y is controlled to be 0.2-5.0mol/L, and the conjugate solution is continuously stirred at the temperature of 20-120 ℃. Generally, the stirring time is 1-120min, and the specific stirring time can be based on the leaching effect of the actual material. And carrying out solid-liquid separation on the leached solution to obtain lead-containing filtrate and insoluble impurities. Preferably, the concentration of X in the conjugate solution is 5 to 15mol/L and the concentration of Y is 0.5 to 5.0 mol/L. More preferably, the concentration of X is 5 to 13mol/L and the concentration of Y is 0.5 to 4.0 mol/L. The reaction temperature is preferably 20 to 100 ℃ and more preferably 20 to 80 ℃.
In step (3) of the method for preparing lead carbonate from lead oxide waste, the lead-containing filtrate and a carbon-containing substance are subjected to contact reaction to obtain lead carbonate and filtrate B. And separating the solution after reaction by centrifugation or filtration to obtain lead carbonate solid and a conjugated solution containing the desulfurization byproduct. In this step, filtrate B can be subjected to desulphatation at reduced temperature and reused in the leaching process of step (2). The carbonaceous substance in the step (3) is one or two selected from carbonate, carbon dioxide or other organic substances capable of decomposing carbon dioxide. Through a large number of tests, the carbonate is one or two of ammonium carbonate, ammonium bicarbonate, sodium carbonate, sodium bicarbonate, potassium carbonate and potassium bicarbonate, and the substance capable of decomposing carbon dioxide is one or two of oxalic acid, acetic acid, formic acid, citric acid, tartaric acid, oxalic acid, malonic acid and urea.
In the carbonization process, the temperature for carbonization is 0-100 ℃ and the time is 0.1-5h, preferably the carbonization reaction temperature is 30-60 ℃ and the carbonization reaction time is 0.2-1 h.
The lead carbonate prepared by the method can be directly used as a product, also can be prepared into high-purity lead oxide by roasting, and meanwhile, the decomposed carbon dioxide can also be returned to the step (3) for recycling.
Detailed Description
To better explain the principles and the inventive aspects of the present invention, the present invention will be further described with reference to the following embodiments.
The present invention first provides a method for preparing a lead sulfate complex, comprising: pre-conversion process of lead oxide waste; a process of catalytic conversion of the crude lead sulfate product; and (3) complexing the X-Y conjugated solution.
When the lead-containing waste contains other non-lead oxide components, a higher content of lead oxide waste can be obtained by a pre-conversion process of the lead-containing waste. Pre-transformation process: the raw materials in the pre-conversion process are lead oxide-containing waste materials, and the main sources are waste battery disassembly lead plaster, waste grid, flue dust, waste lead plaster in the battery preparation process, lithopone leaching residue, lead anode mud, copper converter soot slag, mineral dressing tailings, zinc plant waste residue and the like. In the process, the raw materials contain lead components of Pb, PbO and PbO2And PbSO4Through high-temperature roasting conversion, Pb and PbO in the components are obtained2The reaction takes place to PbO. The final baked product contains Pb and PbSO as main components4。
The specific reaction is as follows:
Pb+PbO2＝2PbO
2Pb+O2＝2PbO
2PbO2＝2PbO+O2
in the process of catalytic vulcanization, the pre-converted lead oxide waste material contains PbO and PbSO4The PbO in the mixed material is converted into lead sulfate by reacting with a sulfuric acid composite solution under the action of a catalyst.
For example, in one implementation process, the pre-converted lead oxide waste is reacted with a mixed solution of sulfuric acid and acetic acid, so that PbO in the pre-converted lead oxide waste reacts with the sulfuric acid to generate lead sulfate, wherein the concentrations of the sulfuric acid and the acetic acid are respectively 3mol/L and 0.3mol/L, the reaction temperature is 105 ℃, and the reaction time is 1.5 h.
In step (1), H2SO4Can be waste liquid of the lead-acid storage battery, new sulfuric acid liquid or a mixture of the waste liquid and the new sulfuric acid liquid. Acetic acid acts primarily catalytically because product H2SO4Is a hardly soluble substance, and lead acetate is a soluble substance, so acetic acid is selected as a catalystThe agent can accelerate the reaction process.
The specific reaction is as follows:
PbO+2CH3COOH＝Pb(CH3COO)2+H2O
Pb(CH3COO)2+H2SO4＝PbSO4+H2O
the overall reaction equation is:
PbO+H2SO4＝PbSO4+H2O
and (2) filtering and separating the reaction solution in the step (1) to obtain lead sulfate and mother liquor containing sulfuric acid and acetic acid. And (4) the obtained crude lead sulfate is ready for use.
And (3) supplementing the consumed sulfuric acid into the mother liquor containing sulfuric acid and acetic acid, and returning the mother liquor subjected to the supplemented sulfuric acid back to the step (1) for recycling.
In the leaching process, since lead sulfate is hardly dissolved in a general solvent or solution, although high-concentration ammonia water can dissolve lead sulfate, the actual solubility is limited. The invention finds that the lead sulfate has good solubility in the X-Y conjugated solution, thereby achieving the purpose of separating the lead sulfate from insoluble impurities by leaching the lead-containing waste under normal pressure.
In the research process, the invention discovers that although many metal impurities such as Ca, Fe, Mn, Cr, Sn, Sb, Bi, Al, Mg and the like are difficult to dissolve in the conjugated complexing agent, some compounds of four metal elements of Cu, Zn, Cd and Ag can be leached to a certain degree. The leaching and carbonization processes can be completed in one step for lead oxide waste materials from waste battery disassembled lead paste, waste grids and waste lead paste in the battery preparation process. For lead oxide waste materials from lithopone leaching slag, lead anode mud, copper converter soot slag, mineral processing tailings, zinc plant waste residue and the like, the invention preferably needs to add PbSO to leached lead sulfate filtrate4By adding PbSO to the lead sulphate filtrate4Crystals are induced to precipitate lead sulfate in the solution, lead sulfate crystals are separated out, and then the lead sulfate crystals are separated from metal impurities to obtain pure lead sulfate, and the pure lead sulfate is separatedDissolving in X-Y conjugate solution to obtain pure lead sulfate solution.
Comprising the addition of PbSO4The step (2) of recrystallization comprises the following steps:
(I) and adding the crude lead sulfate into an X-Y conjugated solution for dissolving, thereby converting solid lead sulfate into a lead sulfate complex. In the conjugate dissolution process of the present invention, it is considered that the following dissolution process may occur, and the reaction formula thereof is represented as follows:
PbSO4+X+H2O＝PbHX(OH)SO4(1)
PbXH(OH)SO4＝PbSO4+X+H2O (2)
wherein the concentration of X in the conjugate solution is 2-15mol/L, the concentration of Y is 0.2-5.0mol/L, the reaction temperature is 20-120 ℃, and the reaction time is 1-120 min.
(II) filtering or centrifuging the reaction solution in the step (I), and adding high-purity PbSO into the filtrate4And crystallizing to separate out the lead sulfate complexed and dissolved in the solution. The crystallization temperature is 0-90 ℃, and the crystallization time is 1-10 h. Preferably, the crystallization temperature is 45 ℃ and the crystallization time is 2 h.
(III) filtering or centrifuging the lead sulfate crystal crystallized in the step (II), and dissolving the lead sulfate crystal in the X-Y conjugated solution to obtain the lead sulfate solution without Cu, Zn, Cd and Ag metal elements. Fig. 1 shows that the method of the present invention further comprises a step of preparing lead carbonate by desulfurization. The steps comprise reacting the prepared lead sulfate complex with a carbonaceous substance, thereby achieving the purpose of preparing lead carbonate.
The invention adopts the composite solution A and the X-Y conjugate solution in the vulcanization process to realize the conversion of the lead oxide-containing waste into the high-concentration lead sulfate solution. The discovery and the use of the novel conjugate complexing agent not only greatly improve the solubility of the lead sulfate, but also provide the basis of liquid phase reaction for the rapid and thorough carbonization process of the subsequent carbonaceous substances. Compared with the reported desulfurization processes of sodium carbonate, ammonium carbonate or sodium hydroxide and the like, the method enables an originally heterogeneous solid-liquid reaction system to be converted into a homogeneous liquid-liquid reaction system, so that the desulfurization of the diachylon is easier to carry out, the desulfurization time is shortened, and the desulfurization rate is greatly increased. Experiments show that the lead sulfate conversion rate of the invention reaches more than 99.5 percent, and the lead carbonization desulfurization rate also reaches 99.9 percent.
The invention adopts the X-Y conjugated solution and carbon-containing substance circulating desulfurization technology, the desulfurizer has relatively low price and is simple and easy to obtain, the reaction solution after desulfurization can be recycled, and the cleanness of the lead-containing waste recovery process is realized to the greatest extent from the atom economy. The existing desulfurization process does not need large-scale equipment improvement, can be directly subjected to automatic production after improvement, and facilitates the industrialization process of a new process.
Embodiments will be described in more detail below with reference to examples. The examples are given solely for the purpose of illustration and are not intended to be limiting.
Example 1
Taking lead oxide waste materials of Zhejiang super-power battery factories. And putting the lead oxide waste into a muffle furnace to be roasted for 0.5h at the temperature of 600 ℃. The roasted lead paste with the main component of lead oxide after roasting is obtained, and the roasted lead paste mainly contains 95 percent of lead oxide (PbO) and the balance of 3 percent of lead sulfate and 2 percent of clay according to physical and chemical measurement. The method comprises the following specific steps:
(1) and (3) vulcanization process: adding 1.00kg of roasted lead oxide waste into a 10L vulcanization reaction kettle, adding 6L of a composite solution of 5.0mol/L sulfuric acid and 1.0mol/L acetic acid into the reaction kettle, controlling the reaction temperature at 70 ℃, stirring at the speed of 300r/min, continuously stirring for 3.0h, and then carrying out solid-liquid separation to obtain 1.33kg of acidified and converted lead sulfate crude product and composite acid mother liquor. PbSO4The crude product was analyzed, wherein PbSO499.5% with the remainder being a solid mixture of very small amounts of insoluble impurities. After the consumed sulfuric acid is supplemented, the composite acid mother liquor is used as the next vulcanization process solution for recycling, and the PbSO is added4The crude product is transferred to the subsequent process for treatment.
(2) And (3) leaching: PbSO obtained in (1)4Adding the crude product into a 20L complex reaction kettle, and adding 10L of X-Y conjugated solution into the reaction kettle, wherein X in the conjugated solution is ethylenediamine with the concentration of8.0mol/L, and Y is the concentration of ammonium bisulfate of 2.0 mol/L. Then stirring is continuously carried out for 10min under the condition of 30 ℃, and the stirring speed is 380 r/min. Then solid-liquid separation is carried out to obtain lead-containing filtrate and insoluble impurities. 10g of high-purity PbSO was added to the filtrate4So that the lead component in the filtrate is converted into PbSO4Crystallizing and separating out, wherein the crystallization temperature is 45 ℃, and the crystallization time is 2 h. Mixing PbSO4Separating the crystal and dissolving again by the X-Y conjugated solution to obtain the complex solution.
(3) And (3) carbonization: transferring the complex solution obtained in the step (2) into a closed carbonization reaction kettle, and controlling the reaction temperature to be 30 ℃ and the stirring speed to be 450 r/min. Sufficient ammonium carbonate was added to the reaction kettle and stirring was continued until no more precipitate was formed. And filtering and separating the reaction mixture to obtain a mixed solution of the lead carbonate precipitate, the conjugated system and ammonium sulfate.
By adopting the recovery method described in the embodiment, 1.14kg of lead carbonate product is finally obtained. The desulfurization rate is 99.97 percent, the lead recovery rate is 98.6 percent and the purity of the prepared lead carbonate is 99.6 percent by calculating through chemical titration.
Example 2
The waste valve-controlled sealed lead-acid battery with the market specification of 12V and 7Ah is crushed and separated by a conventional method to obtain lead paste. And putting the separated lead paste into a muffle furnace to be roasted for 1h at the temperature of 600 ℃. Obtaining the roasted lead paste with the main components of lead oxide and lead sulfate after roasting. The conversion lead plaster is subjected to traditional chemical titration analysis to obtain lead sulfate of 40.2%, lead oxide of 59.4% and other impurities of 0.4%.
The method comprises the following specific steps:
(1) and (3) vulcanization process: adding 1.00kg of the pretreated conversion lead plaster into a 10L vulcanization reaction kettle, adding 6L of a 3.0mol/L sulfuric acid and 1.0mol/L acetic acid composite solution into the vulcanization reaction kettle, controlling the reaction temperature at 80 ℃, stirring at the speed of 300r/min, continuously stirring for 3.0h, and then carrying out solid-liquid separation to obtain the lead plaster after acidification and conversion and filtrate. The mixture obtained after the reaction was filtered to separate 1.21kg of PbSO4Crude product and composite acid mother liquor. PbSO4The crude product was analyzed, wherein PbSO499.6% with the remainder being a solid mixture with a very small amount of insoluble impurities. The composite acid mother liquor is used as the next solution for the vulcanization process after supplementing the consumed sulfuric acid, and the PbSO is used4The crude product is transferred to the subsequent process for treatment.
(2) And (3) leaching: PbSO obtained in (1)4And adding the crude product into a 20L complex reaction kettle, and adding 10L of X-Y conjugated solution into the reaction kettle, wherein X in the conjugated solution is the concentration of ethylenediamine of 7.0mol/L, and Y is the concentration of ammonium sulfate of 2.0 mol/L. Then stirring is continuously carried out for 10min under the condition of 30 ℃, and the stirring speed is 380 r/min. Then solid-liquid separation is carried out to obtain lead-containing filtrate and insoluble impurities.
(3) And (3) carbonization: transferring the lead-containing filtrate obtained in the step (2) into a closed carbonization reaction kettle, adding sufficient sodium carbonate into the reaction kettle under the condition of controlling the reaction temperature to be 20 ℃ and the stirring speed to be 450r/min, and continuously stirring until no precipitate is generated. And filtering and separating the reaction mixture to obtain a mixed solution of the lead carbonate precipitate, the conjugated system and ammonium sulfate.
By adopting the recovery method of the embodiment, 1.06kg of lead carbonate product is finally obtained, and the recovery rate of lead is reduced to 99.5%. The product is obtained by chemical titration analysis method, the desulfurization rate is 99.96%, and the purity of lead carbonate is 99.3%.
Example 3
The lead oxide waste from Zhejiang Congo power supply company is taken. And putting the lead oxide waste into a muffle furnace to be roasted for 0.5h at the temperature of 600 ℃. Obtaining the roasted lead paste with the main components of lead oxide and lead sulfate after roasting, wherein the lead paste mainly contains 95 percent of lead oxide (PbO) through physical and chemical measurement, and the balance of lead sulfate and clay.
The method comprises the following specific steps of:
(1) and (3) vulcanization process: adding 1.00kg of roasted lead oxide waste into a 10L vulcanization reaction kettle, adding 6L of a composite solution of 5.0mol/L sulfuric acid and 1.0mol/L acetic acid into the reaction kettle, controlling the reaction temperature at 70 ℃, stirring at the speed of 300r/min, continuously stirring for 3.0h, and then carrying out solid-liquid separation to obtain 1.33kg of acidified and converted lead sulfate crude product and composite acid mother liquor.PbSO4The crude product was analyzed, wherein PbSO499.6% with the remainder being a solid mixture with a very small amount of insoluble impurities. After the consumed sulfuric acid is supplemented, the composite acid mother liquor is used as the next vulcanization process solution for recycling, and the PbSO is added4The crude product is transferred to the subsequent process for treatment.
(2) And (3) leaching: PbSO obtained in (1)4And adding the crude product into a 20L complex reaction kettle, and adding 10L of X-Y conjugated solution into the reaction kettle, wherein the concentration of X in the conjugated solution is 11.0mol/L, and the concentration of Y in the conjugated solution is 2.0 mol/L. Then stirring is continuously carried out for 10min under the condition of 30 ℃, and the stirring speed is 380 r/min. Then solid-liquid separation is carried out to obtain lead-containing filtrate and insoluble impurities. 10g of high-purity PbSO was added to the filtrate4So that the lead component in the filtrate is converted into PbSO4Crystallizing and separating out, wherein the crystallization temperature is 45 ℃, and the crystallization time is 2 h. Mixing PbSO4Separating the crystal and dissolving again by using the X-Y conjugated solution to obtain a lead-containing solution.
(3) And (3) carbonization: transferring the lead-containing solution obtained in the step (2) into a closed carbonization reaction kettle, and controlling the reaction temperature to be 20 ℃ and the stirring speed to be 450 r/min. And introducing carbon dioxide gas into the reaction kettle until no precipitate is generated. And filtering and separating the reaction mixture to obtain a mixed solution of the lead carbonate precipitate, the conjugated system and ammonium sulfate.
By adopting the recovery method described in the embodiment, 1.18kg of lead carbonate product is finally obtained. The desulfurization rate is 99.95-99.97%, the recovery rate is 99.2%, and the purity of the recovered lead carbonate is 99.2-99.5%.
Example 4
The waste valve-controlled sealed lead-acid battery with the market specification of 12V and 7Ah is crushed and separated by a conventional method to obtain lead paste. And putting the separated lead paste into a muffle furnace to be roasted for 1h at the temperature of 600 ℃. Obtaining the roasted lead paste with the main components of lead oxide and lead sulfate after roasting. The conversion lead plaster is subjected to traditional chemical titration analysis to obtain lead sulfate 40.2%, lead oxide 59.4% and iron and other impurities 0.4%.
The lead-containing waste material comprises the following specific steps:
(1) and (3) vulcanization process: adding 1.00kg of the pretreated conversion lead plaster into a 10L vulcanization reaction kettle, adding 6L of a 2.5mol/L sulfuric acid and 0.5mol/L acetic acid composite solution into the vulcanization reaction kettle, controlling the reaction temperature at 80 ℃, stirring at the speed of 300r/min, continuously stirring for 3.0h, and then carrying out solid-liquid separation to obtain the acidified conversion lead plaster and filtrate. The mixture obtained after the reaction was filtered to separate 1.21kg of PbSO4Crude product and composite acid mother liquor. PbSO4The crude product was analyzed, wherein PbSO499.6% with the remainder being a solid mixture with a very small amount of insoluble impurities. The composite acid mother liquor is used as the next solution for the vulcanization process after supplementing the consumed sulfuric acid, and the PbSO is used4The crude product is transferred to the subsequent process for treatment.
(2) And (3) leaching: PbSO obtained in (1)4Adding the crude product into a 20L complex reaction kettle, and adding 10L of X-Y conjugated solution into the reaction kettle, wherein X in the conjugated solution is 10.0mol/L ammonia, and Y is 2.5mol/L ammonium sulfate. Then stirring is continuously carried out for 10min under the condition of 30 ℃, and the stirring speed is 380 r/min. Then solid-liquid separation is carried out to obtain lead-containing filtrate and insoluble impurities.
(3) And (3) carbonization: transferring the lead-containing filtrate obtained in the step (2) into a closed carbonization reaction kettle, and introducing carbon dioxide gas into the reaction kettle under the condition of controlling the reaction temperature to be 20 ℃ and the stirring speed to be 450r/min for continuous stirring until no precipitate is generated. And filtering and separating the reaction mixture to obtain a mixed solution of the lead carbonate precipitate, the conjugated system and ammonium sulfate.
By adopting the recovery method of the embodiment, 1.06kg of lead carbonate product is finally obtained, the desulfurization rate is 99.97%, the lead recovery rate is 99.1%, and the purity of the prepared lead carbonate is 99.4-99.7%.
Claims (10)
1. A method for preparing lead carbonate from lead oxide waste, which is characterized by comprising the following steps:
(1) and (3) vulcanization: acidifying the lead oxide waste material by using a sulfuric acid composite solution A to obtain a lead sulfate crude product; the sulfuric acid composite solution A is a mixed solution of sulfuric acid and acetic acid;
(2) leaching: dissolving and filtering a lead sulfate crude product obtained by acidification of a sulfuric acid composite solution A by using an X-Y conjugated solution to obtain a lead sulfate filtrate and insoluble impurities; x in the X-Y conjugated solution is organic amine, Y is ammonium salt, the concentration of X in the conjugated solution is 5-13mol/L, and the concentration of Y in the conjugated solution is 0.5-4.0 mol/L;
(3) carbonizing: carrying out contact reaction on the lead sulfate filtrate obtained in the step (2) and a carbon-containing substance to obtain lead carbonate and a filtrate B, wherein the carbon-containing substance is carbon dioxide, carbonate or an organic substance capable of decomposing carbon dioxide; the carbonate is one or two of ammonium carbonate, ammonium bicarbonate, sodium carbonate, sodium bicarbonate, potassium carbonate and potassium bicarbonate, and the organic substance capable of decomposing carbon dioxide is one or two of oxalic acid, acetic acid, formic acid, citric acid, tartaric acid, oxalic acid, malonic acid and urea;
in the carbonization process, the temperature for carbonization is 0-100 ℃, and the time for carbonization is 0.1-5 h;
the step (2) also comprises the step of adding PbSO into the leached lead sulfate filtrate4By adding PbSO to the lead sulphate filtrate4The crystal induces the lead sulfate in the solution to be separated out, the lead sulfate crystal is separated out, then the lead sulfate crystal is separated from the metal impurities to obtain pure lead sulfate, and the pure lead sulfate is dissolved in the X-Y conjugated solution again to obtain a pure lead sulfate solution;
the step (3) further comprises the following steps: and (3) carrying out temperature reduction on the filtrate B to remove sulfate, and using the filtrate B in the leaching process in the step (2) again.
2. The method for preparing lead carbonate from lead oxide waste according to claim 1, wherein in the step (1), the lead oxide waste is added into a reaction kettle, the sulfuric acid composite solution A is added into the reaction kettle, the reaction temperature is controlled to be 20-120 ℃, solid-liquid separation is carried out after continuous stirring is carried out for 0.1-5h, and crude acidified and converted lead sulfate and filtrate are obtained.
3. The method for preparing lead carbonate from lead oxide scrap according to claim 2, wherein the reaction temperature is 20 to 100 ℃.
4. The method for preparing lead carbonate from lead oxide scrap according to claim 2, wherein the reaction temperature is 20 to 80 ℃.
5. The method for preparing lead carbonate from lead oxide waste material according to claim 1, wherein in the step (2), the sulfurized crude lead sulfate is added into the reaction kettle, and sufficient amount of the conjugated solution X-Y is added into the reaction kettle; the X-Y conjugated solution in the step is prepared by mixing X with one or two of ethylenediamine, propylenediamine, ethylenediamine diacetic acid, ethylenediamine tetraacetic acid, propylenediamine diacetic acid, diethanolamine and triethanolamine; y is one or two of ammonium chloride, ammonium bisulfate, ammonium sulfate, ammonium nitrate, ammonium carbonate, ammonium bicarbonate, ammonium monohydrogen phosphate, ammonium dihydrogen phosphate and ammonium phosphate.
6. The method for preparing lead carbonate from lead oxide scrap according to claim 1, wherein the step (2) is carried out under continuous stirring at 20 to 120 ℃.
7. The method for preparing lead carbonate from lead oxide waste according to claim 6, wherein the reaction temperature in the step (2) is 20 to 100 ℃.
8. The method for preparing lead carbonate from lead oxide waste according to claim 1, wherein the carbonization reaction temperature is 30 to 60 ℃ and the carbonization reaction time is 0.2 to 1 hour.
9. A method for preparing lead carbonate from lead oxide waste as claimed in claim 1, wherein said lead oxide waste is selected from the group consisting of: the method comprises the following steps of disassembling lead plaster, waste grids, flue ash, waste lead plaster in the battery preparation process, lithopone leaching residues, lead anode mud, copper converter soot slag, mineral dressing tailings and zinc plant waste residues.
10. The method for preparing lead carbonate from lead oxide waste according to claim 1, wherein the obtained lead carbonate is directly used as a product or is prepared into high-purity lead oxide by roasting, and the decomposed carbon dioxide is returned to the step (3) for recycling.
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| CN110857454B (en) * | 2018-08-23 | 2021-04-23 | 北京化工大学 | A method of recovering lead from lead-containing waste |
| US10968144B2 (en) | 2018-10-08 | 2021-04-06 | Marsulex Environmental Technologies Corporation | Systems and methods for producing potassium sulfate |
| CN109796041B (en) * | 2019-01-22 | 2021-06-29 | 界首市菁华科技信息咨询服务有限公司 | Separation and recycling method of separator in waste lead-acid battery |
| CN111575498A (en) * | 2020-06-19 | 2020-08-25 | 刘洪强 | Chemical treatment method for lead-containing waste |
| CN114990327A (en) * | 2022-05-18 | 2022-09-02 | 济源豫光有色冶金设计研究院有限公司 | Method for resource utilization of waste lead storage battery electrolyte |
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