CN107460339B - A method of recycling lead oxide from waste and old lead acid accumulator lead plaster - Google Patents
A method of recycling lead oxide from waste and old lead acid accumulator lead plaster Download PDFInfo
- Publication number
- CN107460339B CN107460339B CN201710572197.XA CN201710572197A CN107460339B CN 107460339 B CN107460339 B CN 107460339B CN 201710572197 A CN201710572197 A CN 201710572197A CN 107460339 B CN107460339 B CN 107460339B
- Authority
- CN
- China
- Prior art keywords
- lead
- plaster
- waste
- old
- acid
- 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.)
- Active
Links
- 239000011505 plaster Substances 0.000 title claims abstract description 65
- 238000000034 method Methods 0.000 title claims abstract description 62
- 229910000464 lead oxide Inorganic materials 0.000 title claims abstract description 45
- 239000002253 acid Substances 0.000 title claims abstract description 37
- 239000002699 waste material Substances 0.000 title claims abstract description 27
- 238000004064 recycling Methods 0.000 title claims description 14
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 title description 22
- HTUMBQDCCIXGCV-UHFFFAOYSA-N lead oxide Chemical compound [O-2].[Pb+2] HTUMBQDCCIXGCV-UHFFFAOYSA-N 0.000 claims abstract description 69
- 239000008139 complexing agent Substances 0.000 claims abstract description 36
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 28
- 238000011033 desalting Methods 0.000 claims abstract description 26
- 238000010494 dissociation reaction Methods 0.000 claims abstract description 19
- 230000005593 dissociations Effects 0.000 claims abstract description 19
- 238000000926 separation method Methods 0.000 claims abstract description 19
- 239000007788 liquid Substances 0.000 claims abstract description 15
- 150000002500 ions Chemical class 0.000 claims abstract description 13
- RYZCLUQMCYZBJQ-UHFFFAOYSA-H lead(2+);dicarbonate;dihydroxide Chemical compound [OH-].[OH-].[Pb+2].[Pb+2].[Pb+2].[O-]C([O-])=O.[O-]C([O-])=O RYZCLUQMCYZBJQ-UHFFFAOYSA-H 0.000 claims abstract description 4
- 230000003647 oxidation Effects 0.000 claims abstract description 3
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 3
- 238000005406 washing Methods 0.000 claims abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 48
- 238000006243 chemical reaction Methods 0.000 claims description 38
- 239000000243 solution Substances 0.000 claims description 33
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 16
- 238000010612 desalination reaction Methods 0.000 claims description 14
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 12
- 150000003839 salts Chemical class 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 238000004090 dissolution Methods 0.000 claims description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 7
- 229910021529 ammonia Inorganic materials 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 7
- 230000000536 complexating effect Effects 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 6
- PCHPORCSPXIHLZ-UHFFFAOYSA-N diphenhydramine hydrochloride Chemical compound [Cl-].C=1C=CC=CC=1C(OCC[NH+](C)C)C1=CC=CC=C1 PCHPORCSPXIHLZ-UHFFFAOYSA-N 0.000 claims description 5
- GGHDAUPFEBTORZ-UHFFFAOYSA-N propane-1,1-diamine Chemical compound CCC(N)N GGHDAUPFEBTORZ-UHFFFAOYSA-N 0.000 claims description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- 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 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- 229910052787 antimony Inorganic materials 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052718 tin Inorganic materials 0.000 claims description 4
- 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 3
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims description 3
- 239000005695 Ammonium acetate Substances 0.000 claims description 3
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims description 3
- 235000019257 ammonium acetate Nutrition 0.000 claims description 3
- 229940043376 ammonium acetate Drugs 0.000 claims description 3
- 239000000908 ammonium hydroxide Substances 0.000 claims description 3
- 238000000498 ball milling Methods 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- UFYKDFXCZBTLOO-TXICZTDVSA-N 2-amino-2-deoxy-D-gluconic acid Chemical compound [O-]C(=O)[C@H]([NH3+])[C@@H](O)[C@H](O)[C@H](O)CO UFYKDFXCZBTLOO-TXICZTDVSA-N 0.000 claims description 2
- 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 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- 239000000783 alginic acid Substances 0.000 claims description 2
- 229960001126 alginic acid Drugs 0.000 claims description 2
- 235000010443 alginic acid Nutrition 0.000 claims description 2
- 229920000615 alginic acid Polymers 0.000 claims description 2
- 150000004781 alginic acids Chemical class 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 238000010668 complexation reaction Methods 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 2
- 229940043237 diethanolamine Drugs 0.000 claims description 2
- -1 ethyl alcohol Amine Chemical class 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
- 235000019253 formic acid Nutrition 0.000 claims description 2
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 claims description 2
- 239000012528 membrane Substances 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910000069 nitrogen hydride Inorganic materials 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000010008 shearing Methods 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Natural products CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims 1
- 235000019441 ethanol Nutrition 0.000 claims 1
- PIJPYDMVFNTHIP-UHFFFAOYSA-L lead sulfate Chemical compound [PbH4+2].[O-]S([O-])(=O)=O PIJPYDMVFNTHIP-UHFFFAOYSA-L 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 31
- 238000011084 recovery Methods 0.000 abstract description 8
- 230000007613 environmental effect Effects 0.000 abstract description 6
- 238000004140 cleaning Methods 0.000 abstract description 5
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 3
- XOYUVEPYBYHIFZ-UHFFFAOYSA-L diperchloryloxylead Chemical compound [Pb+2].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O XOYUVEPYBYHIFZ-UHFFFAOYSA-L 0.000 abstract description 2
- 229940046892 lead acetate Drugs 0.000 abstract 1
- 230000001376 precipitating effect Effects 0.000 description 16
- 239000000047 product Substances 0.000 description 11
- 239000000203 mixture Substances 0.000 description 9
- 239000003153 chemical reaction reagent Substances 0.000 description 8
- 229910001868 water Inorganic materials 0.000 description 8
- 239000012452 mother liquor Substances 0.000 description 7
- 238000001914 filtration Methods 0.000 description 6
- YADSGOSSYOOKMP-UHFFFAOYSA-N lead dioxide Inorganic materials O=[Pb]=O YADSGOSSYOOKMP-UHFFFAOYSA-N 0.000 description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 5
- 239000002585 base Substances 0.000 description 5
- 239000000706 filtrate Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 238000003723 Smelting Methods 0.000 description 4
- 239000006071 cream Substances 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 229910052924 anglesite Inorganic materials 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 230000001698 pyrogenic effect Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 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 description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- QIVBCDIJIAJPQS-VIFPVBQESA-N L-tryptophane Chemical compound C1=CC=C2C(C[C@H](N)C(O)=O)=CNC2=C1 QIVBCDIJIAJPQS-VIFPVBQESA-N 0.000 description 2
- KDXKERNSBIXSRK-UHFFFAOYSA-N Lysine Natural products NCCCCC(N)C(O)=O KDXKERNSBIXSRK-UHFFFAOYSA-N 0.000 description 2
- 239000004472 Lysine Substances 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- QIVBCDIJIAJPQS-UHFFFAOYSA-N Tryptophan Natural products C1=CC=C2C(CC(N)C(O)=O)=CNC2=C1 QIVBCDIJIAJPQS-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 229960001484 edetic acid Drugs 0.000 description 2
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 2
- XMFOQHDPRMAJNU-UHFFFAOYSA-N lead(II,IV) oxide Inorganic materials O1[Pb]O[Pb]11O[Pb]O1 XMFOQHDPRMAJNU-UHFFFAOYSA-N 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- MTCFGRXMJLQNBG-REOHCLBHSA-N (2S)-2-Amino-3-hydroxypropansäure Chemical compound OC[C@H](N)C(O)=O MTCFGRXMJLQNBG-REOHCLBHSA-N 0.000 description 1
- NAOLWIGVYRIGTP-UHFFFAOYSA-N 1,3,5-trihydroxyanthracene-9,10-dione Chemical compound C1=CC(O)=C2C(=O)C3=CC(O)=CC(O)=C3C(=O)C2=C1 NAOLWIGVYRIGTP-UHFFFAOYSA-N 0.000 description 1
- 239000004475 Arginine Substances 0.000 description 1
- 241001474374 Blennius Species 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 description 1
- 239000004471 Glycine Substances 0.000 description 1
- ONIBWKKTOPOVIA-BYPYZUCNSA-N L-Proline Chemical compound OC(=O)[C@@H]1CCCN1 ONIBWKKTOPOVIA-BYPYZUCNSA-N 0.000 description 1
- ODKSFYDXXFIFQN-BYPYZUCNSA-P L-argininium(2+) Chemical compound NC(=[NH2+])NCCC[C@H]([NH3+])C(O)=O ODKSFYDXXFIFQN-BYPYZUCNSA-P 0.000 description 1
- CKLJMWTZIZZHCS-REOHCLBHSA-N L-aspartic acid Chemical compound OC(=O)[C@@H](N)CC(O)=O CKLJMWTZIZZHCS-REOHCLBHSA-N 0.000 description 1
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 description 1
- HNDVDQJCIGZPNO-YFKPBYRVSA-N L-histidine Chemical compound OC(=O)[C@@H](N)CC1=CN=CN1 HNDVDQJCIGZPNO-YFKPBYRVSA-N 0.000 description 1
- ROHFNLRQFUQHCH-YFKPBYRVSA-N L-leucine Chemical compound CC(C)C[C@H](N)C(O)=O ROHFNLRQFUQHCH-YFKPBYRVSA-N 0.000 description 1
- KDXKERNSBIXSRK-YFKPBYRVSA-N L-lysine Chemical compound NCCCC[C@H](N)C(O)=O KDXKERNSBIXSRK-YFKPBYRVSA-N 0.000 description 1
- FFEARJCKVFRZRR-BYPYZUCNSA-N L-methionine Chemical compound CSCC[C@H](N)C(O)=O FFEARJCKVFRZRR-BYPYZUCNSA-N 0.000 description 1
- COLNVLDHVKWLRT-QMMMGPOBSA-N L-phenylalanine Chemical compound OC(=O)[C@@H](N)CC1=CC=CC=C1 COLNVLDHVKWLRT-QMMMGPOBSA-N 0.000 description 1
- AYFVYJQAPQTCCC-GBXIJSLDSA-N L-threonine Chemical compound C[C@@H](O)[C@H](N)C(O)=O AYFVYJQAPQTCCC-GBXIJSLDSA-N 0.000 description 1
- KZSNJWFQEVHDMF-BYPYZUCNSA-N L-valine Chemical compound CC(C)[C@H](N)C(O)=O KZSNJWFQEVHDMF-BYPYZUCNSA-N 0.000 description 1
- 229910000003 Lead carbonate Inorganic materials 0.000 description 1
- ROHFNLRQFUQHCH-UHFFFAOYSA-N Leucine Natural products CC(C)CC(N)C(O)=O ROHFNLRQFUQHCH-UHFFFAOYSA-N 0.000 description 1
- 239000007832 Na2SO4 Substances 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- ONIBWKKTOPOVIA-UHFFFAOYSA-N Proline Natural products OC(=O)C1CCCN1 ONIBWKKTOPOVIA-UHFFFAOYSA-N 0.000 description 1
- MTCFGRXMJLQNBG-UHFFFAOYSA-N Serine Natural products OCC(N)C(O)=O MTCFGRXMJLQNBG-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- AYFVYJQAPQTCCC-UHFFFAOYSA-N Threonine Natural products CC(O)C(N)C(O)=O AYFVYJQAPQTCCC-UHFFFAOYSA-N 0.000 description 1
- 239000004473 Threonine Substances 0.000 description 1
- KZSNJWFQEVHDMF-UHFFFAOYSA-N Valine Natural products CC(C)C(N)C(O)=O KZSNJWFQEVHDMF-UHFFFAOYSA-N 0.000 description 1
- 235000009754 Vitis X bourquina Nutrition 0.000 description 1
- 235000012333 Vitis X labruscana Nutrition 0.000 description 1
- 235000014787 Vitis vinifera Nutrition 0.000 description 1
- 240000006365 Vitis vinifera Species 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 150000001370 alpha-amino acid derivatives Chemical group 0.000 description 1
- 235000008206 alpha-amino acids Nutrition 0.000 description 1
- 235000001014 amino acid Nutrition 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- ODKSFYDXXFIFQN-UHFFFAOYSA-N arginine Natural products OC(=O)C(N)CCCNC(N)=N ODKSFYDXXFIFQN-UHFFFAOYSA-N 0.000 description 1
- 235000003704 aspartic acid Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- OQFSQFPPLPISGP-UHFFFAOYSA-N beta-carboxyaspartic acid Natural products OC(=O)C(N)C(C(O)=O)C(O)=O OQFSQFPPLPISGP-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 239000003517 fume Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 235000013922 glutamic acid Nutrition 0.000 description 1
- 239000004220 glutamic acid Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 239000004312 hexamethylene tetramine Substances 0.000 description 1
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 1
- HNDVDQJCIGZPNO-UHFFFAOYSA-N histidine Natural products OC(=O)C(N)CC1=CN=CN1 HNDVDQJCIGZPNO-UHFFFAOYSA-N 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 1
- RVPVRDXYQKGNMQ-UHFFFAOYSA-N lead(2+) Chemical compound [Pb+2] RVPVRDXYQKGNMQ-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229930182817 methionine Natural products 0.000 description 1
- 125000000250 methylamino group Chemical group [H]N(*)C([H])([H])[H] 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- COLNVLDHVKWLRT-UHFFFAOYSA-N phenylalanine Natural products OC(=O)C(N)CC1=CC=CC=C1 COLNVLDHVKWLRT-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 239000004474 valine Substances 0.000 description 1
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
- C22B13/00—Obtaining lead
- C22B13/04—Obtaining lead by wet processes
- C22B13/045—Recovery from waste materials
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G21/00—Compounds of lead
- C01G21/02—Oxides
- C01G21/06—Lead monoxide [PbO]
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/54—Reclaiming serviceable parts of waste accumulators
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
-
- 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
-
- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Environmental & Geological Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The present invention relates to the technology for cleaning and recovering fields of old and useless battery, disclose a kind of method that lead oxide is recycled from waste and old lead acid accumulator lead plaster, the following steps are included: 1) pro desalting: lye is added and carries out pro desalting to the lead plaster of waste and old lead acid accumulator, removes lead plumbate, lead acetate, plumbi nitras, lead perchlorate or ceruse in lead plaster；2) dissolve: enveloping agent solution is added into the lead plaster after pro desalting, make wherein all PbO react with complexing agent generation lead complex ion, obtain contain lead solution and filter residue；3) it dissociates: dissociation agent solution is added and adjusts the pH value containing lead solution, dissociates lead complex ion, generate PbO and the mixed liquor containing complexing agent and dissociation agent；4) it separates: being separated by solid-liquid separation, obtains product lead oxide after washing.The method of the present invention process conditions are mild, and technical process environmental protection, process flow is simple, and energy consumption is small, at low cost, and oxidation lead recovery is high, and purity is high has very high industrial application value.
Description
Technical field
The present invention relates to the technology for cleaning and recovering of old and useless battery, more particularly to one kind to return from waste and old lead acid accumulator lead plaster
The method for receiving lead oxide.
Background technique
Lead is one of common metal, and yield occupies the 4th in non-ferrous metal.It is counted according to related data, it is complete at present
The proved reserves of ball lead are used by existing production scale, then through 20~25 years, lead resource will be exhausted.Currently, about 68% lead
It is used to the production process of lead-acid accumulator, lead storage battery passes through long-term charge and discharge process, and capacity drops to very low or grid
Badly damaged when should not repair, battery should just be scrapped.Majority state especially western developed country is paid much attention to from useless in the world
Secondary lead, related data statistics display are recycled in old lead-acid accumulator, the yield of western developed country reviver accounts for about lead total amount
65%, the U.S. is up to 76.2%, and developing country is lower, be lower than 30%, China is only 17.5%.China every year about five or six hundred
Ten thousand lead-acid accumulators generate, and leaded amount of metal is about three, 400,000 tons.
According to statistics, China's lead bullion yield in 2012 has reached 464.6 ten thousand tons, wherein about 3,300,000 tons are used to manufacture plumbic acid
Battery.With the increasingly scarcity of primary lead ore resources, waste lead acid battery has become the primary raw material of reviver industry, how real
The cleaning recycling of existing waste lead acid battery is not only the needs of Environmental security, and realizes that reviver industry value chain urgently solves
Task certainly.Waste lead acid battery mainly includes scrap lead grid and lead plaster at present, and wherein lead plaster accounts for about lead-acid battery consumption of lead
60-65%.For the direct melting recycling lead of better simply scrap lead grid, scrap lead cream contains diversified forms lead and its leaded
Object substance is closed, generally, wherein containing Pb (8-13wt%), PbSO4(35-40wt%), PbO (8-15wt%) and PbO2(35-
40wt%), become the Major Difficulties that existing recycling splicer makees.For a long time, the processing method of domestic and international waste lead accumulator is main
Have: the methods of wet method combined processing of pyrogenic process, wet process, pyrogenic process-, however lead dust, lead steam, the SO generated in pyrometallurgical smelting2Etc. having
Malicious harmful smoke causes serious broken ring to ecological environment.
In order to reduce the smelting temperature and amount of discharged of scrap lead cream smelting process, modern recycling lead just uses wet process
The method of processing usually removes the lead plumbate etc. in lead plaster using sodium carbonate, ammonium hydroxide or sodium hydroxide before entering smelting in advance
Lead salt.A kind of method that lead oxide is recycled from scrap lead cream, mainly molten using complexing agent used in patent CN 104141045A
Liquid carries out dissolution process to the lead plaster after pro desalting, reacts wherein all PbO with complexing agent and generates lead complex ion, obtains
Containing lead solution and filter residue；It is heavy that generation lead salt is reacted with the lead complex ion containing precipitating reagent is added in lead solution to described again
It forms sediment and regenerated complexing agent；The lead salt is precipitated and carries out calcination process, obtains lead oxide, and regenerate the precipitating reagent.It should
The precipitating reagent that method uses is CO2、SO2、SO3One of or it is several.Obtained PbCO3、PbSO3、PbSO4It afterwards, need to also be into
Row roasting obtains lead oxide and regeneration precipitating reagent.Although this method has obtained the lead oxide of high-purity, precipitating reagent is recycled
It utilizes, but secondary method still needs high-temperature roasting, is easy to produce in increase corresponding above of consuming energy, and in roasting
Pb3O4, while the gas generated has higher requirement to the compressive property etc. of reaction kettle, cost is very high.
Application No. is 201610691120 Chinese patents to disclose a kind of method of Whote-wet method recycling lead oxide, does not need
High-temperature roasting can obtain high-purity lead oxide solid, but need to use a large amount of oxidant H during this2O2, price is high, consumption
Greatly, Atom economy is also very poor.
Application No. is 201210535154.1 Chinese patents during recycling lead oxide, improves atom economy benefit
With rate, lead plaster is handled using NaOH, then cooling obtains lead oxide crude product, which is dissolved in NaOH solution again
In recrystallized, obtain pure lead oxide, but the process reaction speed is slower, needs to recrystallize again, and be easy life
At Pb3O4。
Summary of the invention
In order to solve the above-mentioned technical problems, the present invention provides one kind to recycle lead oxide from waste and old lead acid accumulator lead plaster
Method.The method of the present invention process conditions are mild, and technical process environmental protection, process flow is simple, and energy consumption is small, at low cost, lead oxide
The rate of recovery is high, and purity is high has very high industrial application value.
The specific technical solution of the present invention is following steps:
1) pro desalting: being added lye and carry out pro desalting to the lead plaster of waste and old lead acid accumulator, lead plumbate, second in removal lead plaster
Lead plumbate, plumbi nitras, lead perchlorate or ceruse, the lead plaster after obtaining pro desalting；
2) dissolve: enveloping agent solution is added into the lead plaster after pro desalting, make wherein all PbO generation is reacted with complexing agent
Lead complex ion is obtained containing lead solution and filter residue；
3) it dissociates: dissociation agent solution is added and adjusts the pH value containing lead solution, dissociates lead complex ion, generates PbO and contains
The mixed liquor of complexing agent and dissociation agent；
4) it separates: being separated by solid-liquid separation, obtains product lead oxide after washing.
The present invention dissociates lead complex ion by addition dissociation agent, generates PbO precipitating, heavy with addition in the prior art
The principle of shallow lake agent is entirely different, and compared with prior art, dissociation agent does not participate in reaction directly, and Atom economy is high, and solves
PbO from generation is exactly required product, without dissociating agent and complexing agent passing through simple mistake by roasting removal precipitating reagent ingredient
Filter, separation can be recycled, and low energy consumption, simple process, environmental protection.
Preferably, lye described in step 1) is NaOH, KOH, NH3、Ba(OH)2Aqueous solution, weight percent
Concentration is 0.5-40%, and desalination temperature control is at 10-70 DEG C, and the desalination time is 1-60min, and desalination mode is using stirring, shearing
Or ball milling.Desalination reaction can directly occur with above-mentioned alkali and obtain lead oxide and alkali metal salt, alkaline earth gold for lead plumbate in lead plaster
Belong to salt or ammonium salt, reaction equation is as follows, in case where lead salt is lead plumbate, lye is NaOH aqueous solution:
PbSO4+ 2NaOH=PbO+Na2SO4+H2O (1)
Lead plaster is separated by solid-liquid separation after base extraction, lead plaster and desalting mother liquor after obtaining desalination.Lead after desalination
Cream mainly contains the PbO(PbO and PbSO originally intrinsic containing lead plaster4The PbO that equal lead salts are transformed into), Pb and PbO2；And in lead salt
The impurity elements such as acid group, nitrate anion, then enter in desalting mother liquor, realize the separation with lead plaster.
Preferably, the lead plaster after pro desalting described in step 1) needs deionized water to be washed to neutrality.
Preferably, complexing agent described in step 2 is selected from ammonia carboxylic compound, organic amine, hydramine or above-mentioned each substance
Salt.
Preferably, wherein the ammonia carboxylic compound is the compound containing amino and carboxyl simultaneously in molecule, it is selected from α-
Amino acid, ethylenediamine diacetic acid, ethylenediamine tetra-acetic acid, propane diamine oxalic acid, iminodiacetic acid, glucosaminicacid, seaweed
Acid；Wherein the organic amine is selected from methylamine, ethylenediamine, propane diamine, Diethylenetriamine or three second tetramines；Wherein the hydramine is selected from second
Hydramine, diethanol amine or triethanolamine.Wherein α-the amino acid is selected from aspartic acid, methionine, valine, lysine, different
Leucine, phenylalanine, tryptophan, threonine, glycine, proline, histidine, glutamic acid, serine, arginine, flesh ammonia
Acid or citrulling.These complexing agents can occur complexing dissolution with PbO according to reaction equation (2) and react, and wherein R represents complexing agent,
[PbR]2+Lead complex ion is represented, similarly hereinafter.The complexing dissolution phenomena be it is well known in the prior art, repeat no more.
PbO+R+H2O=[PbR]2++2OH- (2)
Preferably, the dissolution is reacted in step 2, Pb and PbO in lead plaster2The two component exists in complexing agent
Under, redox reaction can also occur simultaneously, first generate PbO, then the newly-generated active PbO occurs to be complexed molten with complexing agent
Solution reaction obtains lead complex ion, this that the Pb that existing roasting conversion generates is effectively prevented to the dissolution of PbO selective complexation3O4
Problem.Reaction equation therein can be expressed as follows:
Pb+PbO2=2PbO (3)
PbO+R+H2O=[PbR]2++2OH- (4)
Net reaction are as follows: Pb+PbO2+2R+2H2O=2 [PbR]2++4OH- (5)
Preferably, reaction temperature described in step 2 is 5-120 DEG C.
Reaction is accelerated to carry out preferably, catalyst is added in reaction described in step 2, the catalyst is metal
The combination of one or more of copper, cobalt, the metal powder of nickel or silver or antimonic salt.
Preferably, in step 2, since the pH value of lead oxide complex solution is generally between 5.2-10.3.In lead plaster
On the one hand complexing dissolution cannot occur with above-mentioned complexing agent and react for a variety of amphoteric metal impurity such as Sn, Al and Sb, on the other hand
It is difficult to occur to dissolve significantly in above-mentioned faintly acid or weakly alkaline solution, thus these amphoteric metal impurity enter admittedly
Body residue, it is easy to be realized and (the i.e. water of lead complex ion containing lead solution for example, by conventional solid-liquids separation means such as filterings on ground
Solution) separation.Achieve the purpose that aoxidize improving of lead.
Preferably, dissolved filter residue can be recycled in step 2, to improve lead recovery to greatest extent.
Preferably, dissociation agent described in step 3) is that ammonium acetate, ammonium hydroxide, ammonia, ammonium nitrate, acetic acid, formic acid are water-soluble
The one or more of liquid.
Preferably, the reaction time described in step 3) is in 5-120min, mixing speed 5-120rad/min, reaction
Temperature is at 5-100 DEG C.
After dissociation agent is added, the variation of pH temporarily can make complexing agent lose activity, and destroy lead complex ion, release oxygen
Change lead solid and enveloping agent solution.
It, which is reacted, can be regarded as allowing reaction (2) inversely to carry out.
[PbR]2++2OH-=PbO+R+H2O (6)
Preferably, using separation of solid and liquid, obtaining product lead oxide, and washed using deionized water in step 3)
Until no complexing agent.
Preferably, recycling complexing agent, dissociation agent by the way of circulating condensing or UF membrane in step 4), being back to
Step 2 or 3) middle reuse.Precipitating reagent has obtained separating with complexing agent, and pH value of solution is caused to turn again between 5.2-10.3,
Complexing agent is complexed to obtain complexing lead ion again with lead oxide, realizes the recycling of complexing agent.
It is compared with the prior art, the beneficial effects of the present invention are:
First, Atom economy is high.For the present invention from atom from, the total overall reaction formula of generation is as follows:
Pb+PbO2=2PbO (3)
PbO+R+H2O=[PbR]2++2OH- (4)
[PbR]2++2OH-=PbO+R+H2O (6)
In the case where not bringing other atoms into entire reaction process, all atoms all enter product, do not appoint
What atom discharges, and realizes the Reversible Cycle of whole system.Purification processes, Atom economy have been carried out to lead oxide
It is high.
Second, technical process is more environmentally friendly.The invention avoids the pyrogenic process recycling lead pyrolytic semlting-refining of lead bullion-shot castings-
The processes such as ball milling oxidation, from waste diachylon to product lead oxide, whole process is realized in water phase entirely, does not bring any lead fume
With the discharge of lead dust, the secondary pollution of lead powder dirt and titanium dioxide is not brought, complies fully with green production and energy conservation and environmental protection policy, work
Skill short flow, the rate of recovery are 98.5% or more, and process does not have base stock consumption, and also avoids the use of acid, are avoided
The spent acid of production process discharges, while also avoiding oxidant H2O2Use.The present invention is recycled by the method for Atom economy
Lead oxide can directly obtain the lead oxide that purity is up to 99.90%-99.99%, can satisfy lead-acid battery to high purity oxygen
Change the requirement of lead.Used catalyst, complexing agent, precipitating reagent are all recycled, thus are a kind of economic, efficient, environmental protection
Hydrometallurgic recovery lead plaster directly produces lead oxide method.
Third avoids the pollution of amphoteric metal impurity.Since lead-acid accumulator brings Sn, Al and Sb into while dismantling
Equal amphoteric metals, the presence of the amphoteric metals such as Sn, Al and Sb certainly will influence the quality of product.The complexing agent that the present invention uses, it is right
Dissolution is complexed not generating complexing in these amphoteric metals, but is separated as filter residue with containing lead solution.Reach
The purpose efficiently purified.
4th, process conditions are more energy efficient.Entire link all carries out under aqueous temperature in the present invention, mild condition.Nothing
High-temperature roasting is needed, has saved huge energy consumption, while a large amount of electric energy need not be consumed because of electrorefining.In step 2) of the invention, Pb
With PbO2Normalizing reaction, can only also be carried out, be changed under solution condition at high temperature or in charge and discharge process by traditional
It can be carried out, this makes process conditions of the invention as mild as a dove, and makes the purity of the final products PbO of method of the invention non-
Chang Gao can reach 99.9% or more.
5th, process procedure is simpler.The present invention, using dissociation agent, directly isolates lead oxide solution in step 3),
And it does not need to carry out the ceruse of technique before and product later etc. drying and calcination process, the more supernumerary segment in equipment
It saves, reduces a large amount of equipment and civil engineering investment.
Detailed description of the invention
Fig. 1 is the process flow diagram that the present invention recycles lead oxide from waste diachylon.
Specific embodiment
The invention will be further described with embodiment with reference to the accompanying drawing.
Embodiment 1
According to process flow shown in FIG. 1, waste and old lead acid accumulator lead plaster is taken, the NaOH of excessive 10wt% is then added
For lye, 35 DEG C for the treatment of temperature are controlled, the processing time is 20min, mixing speed 120rad/min.Lead plaster passes through base extraction
Afterwards, it is separated by solid-liquid separation, the lead plaster after obtaining pro desalting and the desalting mother liquor based on sour sodium.Obtained desalination lead plaster is cleaned
Afterwards, 1kg lead plaster is weighed to be added in the first reaction kettle, at the same be added excessive broken stereotype grid, 15g antimony oxide as catalyst,
Enough 0.5mol/L ethylenediamine tetra-acetic acid, propane diamine oxalic acid or its sodium-salt aqueous solutions are as complexing agent, 60 DEG C of conditions of constant temperature
Lower stirring 2h.The mixture obtained after reaction is separated by filtration containing lead solution and filter residue.Wherein it is transferred to described containing lead solution
In second reaction kettle.Enough ammonias are stirred and are continually fed at 50 DEG C of constant temperature, until no longer generating precipitating.And after reacting
Mixture is filtered separation, isolated lead oxide precipitating and the filtrate containing regenerated complexing agent and dissociation agent, by the filter
Liquid, which returns to, to be recycled.
By calculating, its purity of lead oxide product is 99.94%, and the comprehensive recovery of lead is 98.9%.
Embodiment 2
According to process flow shown in FIG. 1, waste and old lead acid accumulator lead plaster is taken, the KOH of excessive 15wt% is then added
For lye, 45 DEG C for the treatment of temperature are controlled, the processing time is 10min, mixing speed 80rad/min.Lead plaster passes through base extraction
Afterwards, it is separated by solid-liquid separation, the lead plaster after obtaining pro desalting and the desalting mother liquor based on sour sodium.Obtained desalination lead plaster is cleaned
Afterwards, 1kg lead plaster is weighed to be added in the first reaction kettle, at the same be added excessive broken stereotype grid, 10g copper oxide as catalyst,
Enough 1mol/L lysine solutions stir 2h under the conditions of 80 DEG C of constant temperature as complexing agent.The mixture that will be obtained after reaction
It is separated by filtration containing lead solution and filter residue.Wherein it is transferred to described in the second reaction kettle containing lead solution.It is stirred at 60 DEG C of constant temperature
And it is continually fed into the hexamethylenetetramine measured in right amount, until no longer generating precipitating.And mixture after reaction is filtered separation,
Isolated lead oxide precipitates and the filtrate containing regenerated complexing agent and dissociation agent, which, which is returned to, recycle makes
With.
By calculating, its purity of lead oxide product is 99.90%, and the comprehensive recovery of lead is 98.5%.
Embodiment 3
According to process flow shown in FIG. 1, waste and old lead acid accumulator lead plaster is taken, is then added excessive 20wt%'s
NH4OH is lye, controls 25 DEG C for the treatment of temperature, the processing time is 30min, mixing speed 90rad/min.Lead plaster passes through lye
It after processing, is separated by solid-liquid separation, the lead plaster after obtaining pro desalting and the desalting mother liquor based on sour sodium.The desalination lead plaster that will be obtained
It after cleaning, weighs 1kg lead plaster and is added in the first reaction kettle, while excessively broken stereotype grid, 15g stannic oxide is added and is used as and urges
Agent, enough 0.5mol/L tryptophan aqueous solutions stir 1h under the conditions of 100 DEG C of constant temperature as complexing agent.It will be obtained after reaction
Mixture be separated by filtration containing lead solution and filter residue.Wherein it is transferred to described in the second reaction kettle containing lead solution.In constant temperature 80
Suitable ammonium acetate is stirred and is continually fed at DEG C, until no longer generating precipitating.And mixture after reaction is filtered separation,
Isolated lead oxide precipitates and the filtrate containing regenerated complexing agent and dissociation agent, which, which is returned to, recycle makes
With.
By calculating, its purity of lead oxide product is 99.93%, and the comprehensive recovery of lead is 99.1%.
Embodiment 4
According to process flow shown in FIG. 1, waste and old lead acid accumulator lead plaster is taken, the Ba of excessive 0.5wt% is then added
(OH)2For lye, 10 DEG C for the treatment of temperature are controlled, the processing time is 60min, mixing speed 5rad/min.Lead plaster passes through lye
It after processing, is separated by solid-liquid separation, the lead plaster after obtaining pro desalting and the desalting mother liquor based on sour sodium.The desalination lead plaster that will be obtained
It after cleaning, weighs 1kg lead plaster and is added in the first reaction kettle, while excessive broken stereotype grid, enough seas 0.5mol/L are added
Alginic acid aqueous solution stirs 2h under the conditions of 5 DEG C of constant temperature as complexing agent.The mixture obtained after reaction is separated by filtration leaded molten
Liquid and filter residue.Wherein it is transferred to described in the second reaction kettle containing lead solution.It stirs and is continually fed into suitable at 80 DEG C of constant temperature
Ammonium nitrate, until no longer generating precipitating.And mixture after reaction is filtered separation, isolated lead oxide precipitates and contains
The filtrate of regenerated complexing agent and dissociation agent, which is returned to and is recycled.
Embodiment 5
According to process flow shown in FIG. 1, waste and old lead acid accumulator lead plaster is taken, the NaOH of excessive 40wt% is then added
For lye, 70 DEG C for the treatment of temperature are controlled, the processing time is 1min, mixing speed 100rad/min.Lead plaster passes through base extraction
Afterwards, it is separated by solid-liquid separation, the lead plaster after obtaining pro desalting and the desalting mother liquor based on sour sodium.Obtained desalination lead plaster is cleaned
Afterwards, it weighs 1kg lead plaster to be added in the first reaction kettle, while excessive broken stereotype grid, enough 0.5mol/L amino Portugals is added
Grape saccharic acid aqueous solution stirs 5min under the conditions of 70 DEG C of constant temperature as complexing agent.The mixture obtained after reaction is separated by filtration
Containing lead solution and filter residue.Wherein it is transferred to described in the second reaction kettle containing lead solution.It stirs and is continually fed at 70 DEG C of constant temperature
Suitable acetic acid, until no longer generating precipitating.And mixture after reaction is filtered separation, isolated lead oxide precipitating and
Filtrate containing regenerated complexing agent and dissociation agent, which is returned to and is recycled.
Raw materials used in the present invention, equipment is unless otherwise noted the common raw material, equipment of this field；In the present invention
Method therefor is unless otherwise noted the conventional method of this field.
The above is only presently preferred embodiments of the present invention, is not intended to limit the invention in any way, it is all according to the present invention
Technical spirit any simple modification, change and equivalent transformation to the above embodiments, still fall within the technology of the present invention side
The protection scope of case.
Claims (8)
1. a kind of method for recycling lead oxide from waste and old lead acid accumulator lead plaster, it is characterised in that comprise the steps of:
1) pro desalting: lye is added, pro desalting is carried out to the lead plaster of waste and old lead acid accumulator, remove lead sulfate, acetic acid in lead plaster
Lead, plumbi nitras or ceruse, the lead plaster after obtaining pro desalting；
2) dissolve: enveloping agent solution is added into the lead plaster after pro desalting, make wherein all PbO reacted with complexing agent generation lead network
Ion is closed, is obtained containing lead solution and filter residue；
3) it dissociates: dissociation agent solution is added and adjusts the pH value containing lead solution, dissociates lead complex ion, generates PbO and containing complexing
The mixed liquor of agent and dissociation agent；
4) it separates: being separated by solid-liquid separation, obtains product lead oxide after washing；
Described in step 3) dissociation agent be ammonium acetate, ammonium hydroxide, ammonia, ammonium nitrate, acetic acid, aqueous formic acid it is a kind of or more
Kind；
Reaction time described in step 3), mixing speed 5-120rad/min, reaction temperature was in 5-100 in 5-120min
℃；
The pH value for the oxidation complexation solution that lead plaster and enveloping agent solution in step 2) obtain is 5.2-10.3, makes amphoteric metal
Sn, Al and Sb do not occur complexing dissolution with complexing agent and react.
2. the method for lead oxide is recycled from waste and old lead acid accumulator lead plaster as described in claim 1, which is characterized in that step
1) lye described in is NaOH, KOH, NH3、Ba(OH)2Aqueous solution, weight percent concentration 0.5-40%, desalination temperature
Control is at 10-70 DEG C, and the desalination time is 1-60min, and desalination mode is using stirring, shearing or ball milling.
3. the method for lead oxide is recycled from waste and old lead acid accumulator lead plaster as claimed in claim 1 or 2, which is characterized in that
Lead plaster after pro desalting described in step 1) needs deionized water to be washed to neutrality.
4. the method for lead oxide is recycled from waste and old lead acid accumulator lead plaster as described in claim 1, which is characterized in that step
2) complexing agent described in be selected from ammonia carboxylic compound, methylamine, ethylenediamine, propane diamine, Diethylenetriamine, three second tetramines, hydramine or on
State the salt of each substance.
5. the method for lead oxide is recycled from waste and old lead acid accumulator lead plaster as claimed in claim 4, which is characterized in that wherein
The ammonia carboxylic compound is the compound containing amino and carboxyl simultaneously in molecule, is selected from a-amino acid, ethylenediamine diacetic acid, second
Ethylenediamine tetraacetic acid (EDTA), propane diamine oxalic acid, iminodiacetic acid, glucosaminicacid, alginic acid；Wherein the hydramine is selected from ethyl alcohol
Amine, diethanol amine or triethanolamine.
6. the method as described in claim 1 or 4 for recycling lead oxide from waste and old lead acid accumulator lead plaster, which is characterized in that
Reaction temperature described in step 2) is 5-120 DEG C.
7. the method as described in claim 1 or 4 for recycling lead oxide from waste and old lead acid accumulator lead plaster, which is characterized in that
Reaction described in step 2) be added catalyst accelerate reaction carry out, the catalyst be metallic copper, cobalt, nickel, silver powder and
The combination of one or more of antimonic salt.
8. the method for lead oxide is recycled from waste and old lead acid accumulator lead plaster as described in claim 1, which is characterized in that step
4) in, complexing agent, dissociation agent are recycled by the way of circulating condensing or UF membrane, are back to step 2) or 3) middle reuse.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710572197.XA CN107460339B (en) | 2017-07-13 | 2017-07-13 | A method of recycling lead oxide from waste and old lead acid accumulator lead plaster |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710572197.XA CN107460339B (en) | 2017-07-13 | 2017-07-13 | A method of recycling lead oxide from waste and old lead acid accumulator lead plaster |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107460339A CN107460339A (en) | 2017-12-12 |
| CN107460339B true CN107460339B (en) | 2019-08-27 |
Family
ID=60546291
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710572197.XA Active CN107460339B (en) | 2017-07-13 | 2017-07-13 | A method of recycling lead oxide from waste and old lead acid accumulator lead plaster |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107460339B (en) |
Families Citing this family (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108232351B (en) * | 2018-01-29 | 2020-06-09 | 长沙理工大学 | A comprehensive recycling method for waste ternary lithium-ion power batteries |
| CN111170360B (en) * | 2018-11-13 | 2023-12-12 | 湖南省金翼有色金属综合回收有限公司 | Device and process for preparing lead oxide from desulfurization lead |
| CN111170358B (en) * | 2018-11-13 | 2023-11-28 | 湖南省金翼有色金属综合回收有限公司 | Device and process for preparing lead oxide from lead paste of waste lead-acid storage battery |
| CN111549235A (en) * | 2019-02-08 | 2020-08-18 | 北京中金瑞丰环保科技有限公司 | Separation method of lead-containing raw material |
| CN111172395A (en) * | 2019-10-23 | 2020-05-19 | 超威电源集团有限公司 | Method for preparing lead oxide from waste lead paste |
| TWI700849B (en) * | 2019-10-29 | 2020-08-01 | 中華學校財團法人中華科技大學 | Utilizing recycled lead-acid batteries to produce perovskite quantum dots and method |
| CN111302388B (en) * | 2020-02-22 | 2023-08-15 | 南京信息工程大学 | A kind of preparation method of spherical lead oxide atmospheric mineral dust |
| CN112551573A (en) * | 2020-09-03 | 2021-03-26 | 蚌埠睿德新能源科技有限公司 | Preparation method of lead oxide |
| CN112442602A (en) * | 2020-10-09 | 2021-03-05 | 超威电源集团有限公司 | Waste lead plaster recovery method |
| CN112426796A (en) * | 2020-11-16 | 2021-03-02 | 张克军 | System for purifying and recycling complexing liquid for recycling lead oxide |
| CN112694118A (en) * | 2020-12-09 | 2021-04-23 | 超威电源集团有限公司 | Preparation method of red lead |
| CN113621812B (en) * | 2021-08-17 | 2022-11-08 | 太和县大华能源科技有限公司 | Lead oxide preparation process based on waste lead-acid storage battery lead plaster |
| CN114606393A (en) * | 2022-01-26 | 2022-06-10 | 超威电源集团有限公司 | Waste lead paste recovery method |
| CN114709419A (en) * | 2022-02-28 | 2022-07-05 | 浙江铅锂智行科技有限公司 | Device and method for preparing anode lead paste additive |
| CN115369257A (en) * | 2022-07-12 | 2022-11-22 | 超威电源集团有限公司 | Solvent-circulated waste lead paste recovery method |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4322781A1 (en) * | 1993-07-08 | 1995-01-12 | Varta Batterie | Process for the treatment of waste water from the production of lead accumulators |
| CN102689922B (en) * | 2011-03-24 | 2017-04-19 | 杨春晓 | Lead compound nano-powder preparation method for recovery and manufacture of lead-acid battery |
| CN102689921B (en) * | 2011-03-24 | 2017-08-08 | 杨春晓 | The preparation method for the Pb nm-class oxide powders for reclaiming and manufacturing for lead-acid accumulator |
| CN103526016B (en) * | 2012-07-02 | 2015-11-04 | 张超 | A kind of method of raw material containing lead hydrometallurgic recovery |
| CN108018423A (en) * | 2014-01-16 | 2018-05-11 | 北京化工大学 | A kind of method that lead oxide is recycled from the scrap lead containing oxidation |
| CN104141045B (en) * | 2014-08-20 | 2017-04-12 | 北京化工大学 | Method for recovering lead oxide from waste lead plaster |
| CN106587142B (en) * | 2016-11-23 | 2017-12-29 | 超威电源有限公司 | A kind of method that 4BS is prepared using waste lead acid battery lead cream |
-
2017
- 2017-07-13 CN CN201710572197.XA patent/CN107460339B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN107460339A (en) | 2017-12-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107460339B (en) | A method of recycling lead oxide from waste and old lead acid accumulator lead plaster | |
| CN104141045B (en) | Method for recovering lead oxide from waste lead plaster | |
| CN101509071B (en) | Method for recovering valuable metals from lithium battery slag containing Co, Ni, Mn | |
| CN102285673B (en) | Method for recovering lithium and iron from lithium iron phosphate power battery for electromobile | |
| CN103103360B (en) | Method for recovering copper, tungsten and molybdenum by use of APT (ammonium paratungstate) waste slag | |
| CN110857454B (en) | A method of recovering lead from lead-containing waste | |
| CN109055757B (en) | Method for recovering manganese dioxide and lead in anode slag of electrolytic manganese or electrolytic zinc | |
| CN109136571B (en) | Method for extracting valuable metals from lithium ion battery mixed manganese-rich waste leachate | |
| CN104789776A (en) | A method for recovering lead oxide from waste containing lead oxide | |
| CN105958148A (en) | Method for recovering valuable metal from waste lithium nickel cobalt manganese oxide battery material | |
| CN103966446A (en) | Method for separating and recovering copper, nickel and iron from electroplating sludge | |
| CN103031437B (en) | Processing method for waste liquid from stripping tin scolding | |
| CN106435197A (en) | Process and device for alkaline extraction and recovery from waste catalysts in SCR (selective catalytic reduction) denitrification | |
| CN111180819A (en) | A kind of preparation method of battery grade Ni-Co-Mn mixed solution and battery grade Mn solution | |
| CN111697282A (en) | Method for extracting lithium from dilute solution recovered from waste battery positive electrode material | |
| CN109929997A (en) | A method of germanium concentrate is produced with N235 extractant | |
| CN107779603A (en) | A kind of method that ceruse is prepared in the scrap lead from oxidation | |
| CN104862487B (en) | A kind of resource high-efficiency method for transformation of non-ferrous metal zinc metallurgy flying dust | |
| CN115491496B (en) | A method for selective separation of cobalt, manganese, zinc and cadmium by hydrometallurgy zinc smelting purification cobalt slag | |
| CN105907986A (en) | Extracting method for lead in silver separating residues | |
| CN101603125A (en) | A kind of method of purification and impurity removal of nickel liquid | |
| CN117512342B (en) | Method for recycling lithium from waste ternary lithium ion battery anode material | |
| CN107630147B (en) | Method for removing chloride ions in electrolytic manganese solution | |
| CN112481493A (en) | Method for recovering valuable metals from ternary positive electrode materials of waste power batteries | |
| CN101713025B (en) | Method for wet separation of mixed solution containing nickel and zinc |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CP01 | Change in the name or title of a patent holder |
Address after: 313100 Zhejiang city of Huzhou province Changxing County pheasant emerging urban industrial park Patentee after: Chaowei Power Group Co., Ltd Address before: 313100 Zhejiang city of Huzhou province Changxing County pheasant emerging urban industrial park Patentee before: Chilwee Power Supply Co., Ltd. |
|
| CP01 | Change in the name or title of a patent holder |