CN105197987A - Separation method of PbO, PbSO4 and PbO2 mixture - Google Patents
Separation method of PbO, PbSO4 and PbO2 mixture Download PDFInfo
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- CN105197987A CN105197987A CN201510731341.0A CN201510731341A CN105197987A CN 105197987 A CN105197987 A CN 105197987A CN 201510731341 A CN201510731341 A CN 201510731341A CN 105197987 A CN105197987 A CN 105197987A
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- pbo
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- liquid
- lead
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Links
- 238000000926 separation method Methods 0.000 title claims abstract description 291
- 239000000203 mixture Substances 0.000 title claims abstract description 74
- YADSGOSSYOOKMP-UHFFFAOYSA-N lead dioxide Inorganic materials O=[Pb]=O YADSGOSSYOOKMP-UHFFFAOYSA-N 0.000 title claims abstract description 12
- YEXPOXQUZXUXJW-UHFFFAOYSA-N lead(II) oxide Inorganic materials [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 title abstract description 201
- 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 title abstract 4
- 229910052924 anglesite Inorganic materials 0.000 title abstract 4
- 239000000463 material Substances 0.000 claims abstract description 275
- 239000007788 liquid Substances 0.000 claims abstract description 223
- 238000000034 method Methods 0.000 claims abstract description 194
- 230000008569 process Effects 0.000 claims abstract description 119
- 238000002386 leaching Methods 0.000 claims abstract description 99
- 239000011505 plaster Substances 0.000 claims abstract description 57
- 239000002699 waste material Substances 0.000 claims abstract description 44
- 239000002253 acid Substances 0.000 claims abstract description 43
- 239000000047 product Substances 0.000 claims abstract description 35
- 239000002994 raw material Substances 0.000 claims abstract description 27
- 238000007670 refining Methods 0.000 claims abstract description 20
- 238000010168 coupling process Methods 0.000 claims abstract description 13
- 238000005406 washing Methods 0.000 claims description 119
- 239000012535 impurity Substances 0.000 claims description 95
- 239000007790 solid phase Substances 0.000 claims description 87
- 239000007791 liquid phase Substances 0.000 claims description 83
- 239000003795 chemical substances by application Substances 0.000 claims description 60
- 238000000746 purification Methods 0.000 claims description 60
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 51
- 238000002425 crystallisation Methods 0.000 claims description 44
- 238000004064 recycling Methods 0.000 claims description 41
- -1 hexafluorosilicic acid Chemical compound 0.000 claims description 32
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 30
- 238000001035 drying Methods 0.000 claims description 25
- 230000008025 crystallization Effects 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 239000002904 solvent Substances 0.000 claims description 22
- 238000004090 dissolution Methods 0.000 claims description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 18
- 238000001816 cooling Methods 0.000 claims description 18
- 150000003839 salts Chemical class 0.000 claims description 18
- 238000001704 evaporation Methods 0.000 claims description 17
- 230000008020 evaporation Effects 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 230000006837 decompression Effects 0.000 claims description 15
- 238000004042 decolorization Methods 0.000 claims description 14
- 239000012071 phase Substances 0.000 claims description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- 239000002808 molecular sieve Substances 0.000 claims description 10
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 10
- 239000006002 Pepper Substances 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 150000002500 ions Chemical class 0.000 claims description 8
- 239000012452 mother liquor Substances 0.000 claims description 8
- 239000012808 vapor phase Substances 0.000 claims description 8
- 230000009615 deamination Effects 0.000 claims description 7
- 238000006481 deamination reaction Methods 0.000 claims description 7
- 239000003463 adsorbent Substances 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims description 4
- 239000002594 sorbent Substances 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims 1
- 238000005516 engineering process Methods 0.000 abstract description 35
- 238000003860 storage Methods 0.000 abstract description 27
- 238000002360 preparation method Methods 0.000 abstract description 14
- 239000006227 byproduct Substances 0.000 abstract description 11
- 230000002829 reductive effect Effects 0.000 abstract description 10
- 230000008878 coupling Effects 0.000 abstract description 3
- 238000005859 coupling reaction Methods 0.000 abstract description 3
- 229910010272 inorganic material Inorganic materials 0.000 abstract description 2
- 238000005554 pickling Methods 0.000 abstract description 2
- 150000002484 inorganic compounds Chemical class 0.000 abstract 1
- HTUMBQDCCIXGCV-UHFFFAOYSA-N lead oxide Chemical compound [O-2].[Pb+2] HTUMBQDCCIXGCV-UHFFFAOYSA-N 0.000 description 202
- 239000000243 solution Substances 0.000 description 68
- 238000011084 recovery Methods 0.000 description 27
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 26
- 238000006243 chemical reaction Methods 0.000 description 20
- 239000013543 active substance Substances 0.000 description 18
- 238000004070 electrodeposition Methods 0.000 description 18
- 239000011734 sodium Substances 0.000 description 17
- 229910052751 metal Inorganic materials 0.000 description 15
- 239000002184 metal Substances 0.000 description 15
- 238000003756 stirring Methods 0.000 description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 14
- 230000001698 pyrogenic effect Effects 0.000 description 14
- 239000007789 gas Substances 0.000 description 12
- 238000004519 manufacturing process Methods 0.000 description 12
- 230000008901 benefit Effects 0.000 description 11
- PIJPYDMVFNTHIP-UHFFFAOYSA-L lead sulfate Chemical compound [PbH4+2].[O-]S([O-])(=O)=O PIJPYDMVFNTHIP-UHFFFAOYSA-L 0.000 description 11
- 239000000843 powder Substances 0.000 description 11
- 238000003723 Smelting Methods 0.000 description 10
- 239000008151 electrolyte solution Substances 0.000 description 10
- 238000005265 energy consumption Methods 0.000 description 10
- 238000006477 desulfuration reaction Methods 0.000 description 9
- 238000006722 reduction reaction Methods 0.000 description 9
- 230000023556 desulfurization Effects 0.000 description 8
- 230000005518 electrochemistry Effects 0.000 description 8
- 229910052745 lead Inorganic materials 0.000 description 8
- 238000001556 precipitation Methods 0.000 description 8
- 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 7
- 229910052799 carbon Inorganic materials 0.000 description 7
- 235000003599 food sweetener Nutrition 0.000 description 7
- 238000007254 oxidation reaction Methods 0.000 description 7
- 238000004062 sedimentation Methods 0.000 description 7
- 239000003765 sweetening agent Substances 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 6
- 238000000151 deposition Methods 0.000 description 6
- 229910000464 lead oxide Inorganic materials 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 230000003068 static effect Effects 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 239000006071 cream Substances 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- MFEVGQHCNVXMER-UHFFFAOYSA-L 1,3,2$l^{2}-dioxaplumbetan-4-one Chemical compound [Pb+2].[O-]C([O-])=O MFEVGQHCNVXMER-UHFFFAOYSA-L 0.000 description 4
- 229910000003 Lead carbonate Inorganic materials 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 4
- 238000001354 calcination Methods 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 238000002203 pretreatment Methods 0.000 description 4
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 239000000428 dust Substances 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000003672 processing method Methods 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000001509 sodium citrate Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 description 3
- 229940038773 trisodium citrate Drugs 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 240000006909 Tilia x europaea Species 0.000 description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 2
- 235000011130 ammonium sulphate Nutrition 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 238000005272 metallurgy Methods 0.000 description 2
- 230000008439 repair process Effects 0.000 description 2
- 238000012827 research and development Methods 0.000 description 2
- 239000002893 slag Substances 0.000 description 2
- 239000001117 sulphuric acid Substances 0.000 description 2
- 235000011149 sulphuric acid Nutrition 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 230000001131 transforming effect Effects 0.000 description 2
- 238000010977 unit operation Methods 0.000 description 2
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 1
- 239000005695 Ammonium acetate Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229940043376 ammonium acetate Drugs 0.000 description 1
- 235000019257 ammonium acetate Nutrition 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000002802 bituminous coal Substances 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000567 combustion gas Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 238000007499 fusion processing Methods 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 238000009854 hydrometallurgy Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 150000002611 lead compounds Chemical class 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000010327 methods by industry Methods 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000009853 pyrometallurgy Methods 0.000 description 1
- 238000003908 quality control method Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 230000002000 scavenging effect Effects 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000000844 transformation Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G21/00—Compounds of lead
- C01G21/20—Sulfates
-
- 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
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G21/00—Compounds of lead
- C01G21/02—Oxides
- C01G21/08—Lead dioxide [PbO2]
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G21/00—Compounds of lead
- C01G21/003—Preparation involving a liquid-liquid extraction, an adsorption or an ion-exchange
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention relates to a separation method of a PbO, PbSO4 and PbO2 mixture, in particular to a process and a technology of resource comprehensive utilization of a lead containing material of a waste lead storage battery, and belongs to the technical field of comprehensive utilization of three wastes of the waste lead storage battery or separation and refining of inorganic compounds. The separation method comprises steps as follows: PbO, PbSO4 and PbO2 mixture containing lead plaster obtained from the lead containing material, treated with a physical separation method, of the waste lead storage battery is taken as a raw material, the raw material is treated with technologies including acid pickling dissolving, leaching dissolving, separation, refining and solid-liquid separation coupling, and separation of the PbO, PbSO4 and PbO2 mixture is realized. The process is reasonable, the preparation method is simple, the purity and the yield of products are high, by-products in the process are greatly reduced, the comprehensive utilization cost of the lead plaster resource is reduced, the process is safe and reliable, and large-scale industrialization is facilitated.
Description
Technical field
The present invention relates to the processing method that a kind of waste lead accumulator lead is recycled, what specifically obtain through physical separation method process with the lead-containing material of waste lead accumulator contains PbO, PbSO
4, PbO
2the lead plaster of mixture is raw material, adopts acidleach to dissolve, leaches dissolving, separation and purification, solid-liquid separation coupling technique, realize PbO, PbSO
4, PbO
2the separation of mixture.
Belong to three-protection design and application technology as the second resource field, especially Comprehensive Utilization of Waste Lead Accumulator technical field; Also technical field of chemical separation is belonged to; Also the preparing technical field of inorganic materials is belonged to.
Background technology
1. the lead resourceization of waste lead accumulator is recycled
1.1 lead storage battery
The major parts of lead storage battery is positive plate, negative plate, electrolytic solution, barrier film or dividing plate, battery jar, in addition, also has some parts as terminal, connecting strip, blow-off pet cock etc.Lead storage battery has the advantages such as structure is simple, easy to use, dependable performance, price are low, is the product of large, the applied range of output in chemical power source always.Along with research and development and the application of novel material and new technology, the properties of lead storage battery has had and has increased substantially, lead storage battery manifests more in the advantage of some special application fields, and as Moped Scooter, extraordinary power truck, new automobile power supply, the nearly stage is still main flow power supply.
1.2 waste lead accumulator
In use, through long-term charge and discharge process, capacity drops to very low or grid corrosion when being seriously difficult to repair to lead storage battery, and lead storage battery normally cannot carry out charge/discharge operation, thus produce waste lead accumulator.Because lead storage battery improper use causes damaging, also waste lead accumulator can be produced.
Reason that what lead storage battery was common scrap has active substance softening and shedding etc. on the sulphating of pole plate, grid corrosion, pole plate.Wherein the sulphating of pole plate is on pole plate, generate the hard lead sulfate crystal spot of white, is very difficult to again be converted into active substance, does not reach the object charged normal during charging, and the sulphating of lead storage battery modally scraps reason.
The importance that 1.3 waste lead accumulator lead resourceizations are recycled
The structure of waste lead accumulator is substantially identical with lead storage battery with composition.As forming the main composition material-lead of lead storage battery, be one of conventional metal, its output, after iron, copper, aluminium, zinc metal, occupies the 5th.At present, the lead of about 70% is for the preparation of lead storage battery, and lead plaster is actually PbO, PbSO that the painting cream in store battery is formed after changing into and using
4, PbO
2in the mixture of composition, its composition and content depend on cycle index and the life-span length of waste lead accumulator.
Therefore, from waste lead accumulator, recycle lead is extremely important lead source.Sufficiently and reasonably utilize the lead resource of waste lead accumulator, not only can alleviate the situation that lead resource falls sharply day by day, also can reduce preparation cost simultaneously, reduce environmental pollution.So, realize the recycling of the lead of waste lead accumulator, not only there is the strategic importance of Sustainable development, and there is important economy and social value.
2. the process technologies of existing lead resourceization recycling
The lead plaster that waste lead accumulator obtains after sorting and pre-treatment is most important lead-containing compounds, and in lead plaster, main component is roughly: 45%-65%PbSO
4, 10%-30%PbO, 10%-20%PbO
2with the mixture of 2%-3% metallic lead, wherein PbSO in lead plaster
4content reaches more than 50%.
From the disposal and utilization problem of the technique of waste lead battery lead recovery and technology mainly lead plaster, namely the treatment process of lead-containing compounds in lead plaster, mainly contains: pyrogenic process, wet method, pyrogenic process-wet method coupled processing method etc. at present.The process technologies that existing lead resourceization is recycled is discussed below respectively:
The plumbous recovery technology of 2.1 pyrometallurgical smeltings
2.1.1 the plumbous recovery technology of direct pyrometallurgical smelting
Direct pyrogenic process lead smelting recovery technology dominating process route is: PbO, PbSO of directly obtaining after sorting and pre-treatment with waste lead accumulator
4, PbO
2mixture is raw material, obtains metallic lead and lead oxides through Overheating Treatment.Because PbSO
4fusing point is high, and reaching the temperature of decomposing completely will more than 1000 DEG C, usually with combustion gas, fuel oil, bituminous coal etc. for fuel, in high temperature melting furnace, at the furnace temperature of 1260 DEG C-1316 DEG C, melting obtains metallic lead.
The advantage of direct pyrogenic process lead smelting recovery process is that operating unit is few.Shortcoming is because smelting temperature is high, reaches about 1300 DEG C from kiln gas temperature, and process energy consumption is large; Cause a large amount of lead volatility to lose under high temperature and form the lead dust of contaminative; The SO produced in fusion process
2concentration is high, seriously polluted; SO
2tail gas pollution environment.Metal recovery rate generally only has 80%-85% simultaneously, and the lead tolerance of slag reaches more than 10%.Unreasonable disposal in waste lead accumulator regenerative process also can produce the secondary pollution to environment, and causes the low inferior wasting of resources phenomenon of level of comprehensive utilization.
2.1.2 the plumbous recovery technology of the pyrogenic process improved
In order to overcome the shortcomings such as the pyrogenic process regeneration high energy consumption of melting, metallic lead volatilization loss amount are large, seriously polluted, have developed lead plaster desulfurization conversion technique, the plumbous recovery process of the pyrogenic process namely improved.Lead sulfate (is generally converted into lead carbonate by other compound that first lead sulfate is converted into easier pyrogenic attack by this technique, because the fusing point of lead carbonate is more much lower than lead sulfate, because lead carbonate just can be decomposed into yellow lead oxide at 340 DEG C, therefore pyrometallurgical smelting can be carried out at a lower temperature, sulfate radical in lead sulfate is converted into water-soluble vitriol, i.e. " desulfurization conversion " method simultaneously.Conventional sweetening agent is (NH
4)
2cO
3, NH
4hCO
3, Na
2cO
3, NaHCO
3, NaOH etc., by the PbSO in lead plaster
4be converted into solvable Na
2sO
4and insoluble Pb
2cO
3or Pb (OH)
2precipitation.Na in filtrate
2sO
4, (NH
4)
2sO
4na is obtained after cooling
2sO
410H
2o or (NH
4)
2sO
4crystal is the by product of process.
The pyrogenic process of improvement reclaims splicer skill due to PbCO
3for main raw material, therefore, significantly can reduce smelting temperature, decrease SO
2pollute, improve operating environment.Its main drawback in desulfurization conversion process, there is desulfurization conversion be difficult to carry out problem thoroughly, generally has the PbSO of about 5%
4in residual lead plaster in post-conversion, in melting, still SO can be produced
2discharge.Employing carbonate is sweetening agent, produces a large amount of sulfate by-products in process, certainly exists the recycling problem of vitriol, and still there is the problems such as the low and energy expenditure of plumbous recovery utilization rate is large in process.
The plumbous recovery technology of 2.2 wet methods
In order to solve the problem in the plumbous recovery technology of pyrogenic process, from the 1950's, have developed the plumbous recovery technology of wet method.The core of the plumbous recovery technology of wet method utilizes the Pb dissolved in the solution
2+generating metal Pb in negative electrode generation reduction reaction, thus realize plumbous recovery, is a kind of environmentally friendly plumbous recovery technology.According to the feature of technological process, hydrometallurgic recovery smelting technology is divided into Direct Electrochemistry sedimentation and indirect electrochemical sedimentation.
2.2.1 Direct Electrochemistry sedimentation
Direct Electrochemistry sedimentation is directly placed in electrochemical reactor by lead plaster, reclaims obtain lead through electrochemical deposition.Typical Direct Electrochemistry sedimentation is the technology that yellow lead oxide in a kind of NaOH of the employing aqueous dissolution lead plaster researched and developed by Chinese Academy Of Sciences Process Engineering Research Institute (former chemical industry metallurgical institute) prepares the leaded aqueous solution.This technique is using the 10%-15%NaOH aqueous solution as electrolytic solution electrolytic solution, and be carry out electrochemical deposition under the condition of 1.8-2.6V at bath voltage, negative electrode generation reduction reaction obtains metallic lead, and lead recovery is greater than 95%, and current efficiency can reach 85%.
The subject matter that this technique exists is that power consumption is high, because the reduction reaction only having negative electrode to occur is effecting reaction, energy expenditure is 350kWh/tPb, and alkaline consumption is 100kgNaOH/tPb.
2.2.2 indirect electrochemical sedimentation
Due to PbSO in lead plaster
4, PbO
2existence, most of electrochemical deposition method technique cannot Direct Electrochemistry depositing treatment lead plaster, need carry out electrochemical deposition method process again after further transforming, leaching process.
In indirect electrochemical sedimentation process lead plaster technique, typically there are RSR technique, USBM technique, CX-EW technique, NaOH-KNaC
4h
4o
6technique etc.The something in common of these techniques is first by PbSO
4and PbO
2transform, then leaching process is carried out to lead plaster, finally adopt electrochemical deposition method to obtain highly purified lead.Main technique has:
(1) RSR indirect electrochemical depositing operation
The core technology of RSR technique is: (NH
4)
2cO
3desulfurization-Na
2sO
3conversion-H
2siF
4dissolving-electrochemical cathode reduces.Adopt (NH
4)
2cO
3the PbSO in lead plaster is made for sweetening agent
4desulfurization conversion is PbCO
3precipitation, with SO
2gas or sulphite are the PbO in reductive agent and lead plaster solution
2there is reduction reaction and generate PbO precipitation, with the HBF of about 20%
4or H
2siF
6solution is the PbCO that leaching liquid will obtain
3in solution, make electrolytic solution with the leaching of PbO precipitation, then contain Pb by what obtain
2+electrochemical deposition is carried out after the further removal of impurities process of leaching liquid.In electrochemical deposition process, general employing graphite or coating PbO
2titanium plate etc. as insoluble anode, the metals such as plumbous or stainless steel plate are negative electrode.During electrolysis, on negative electrode, precipitating metal is plumbous, because hydrogen overvoltage is higher, therefore H occurs
+the side reaction of electrochemical reduction is fewer; Anode mainly separates out O
2but, have part Pb
2+on anode, electrochemical oxidation generates PbO
2.PbO is separated out in order to reduce on anode
2, must manage to reduce oxygen deposition potential, or add some valence variation element (as P, As, Co) in the electrolytic solution to reduce PbO
2growing amount.The bath voltage of electrochemical deposition operation is about 2.2V, actuating current density is 200A/m
2-300A/m
2, can obtain purity at negative electrode and be greater than 99.99% metallic lead, general cathode efficiency can reach more than 90%.
(2) USBM indirect electrochemical depositing operation
The core technology of USBM technique is: (NH
4)
2cO
3desulfurization-metal Pb conversion-H
2siF
4dissolving-electrochemical cathode reduces.USBM technique is substantially identical with RSR technique, utilizes ammonium sulfate the lead sulfate desulfurization conversion in lead plaster to be precipitated for lead carbonate for sweetening agent equally.Difference take lead powder as PbO in reductive agent and lead plaster solution
2there is reduction reaction and generate PbO precipitation, PbO and the PbCO of generation
3use H
2siF
6electrolytic solution is made in dissolving, then carries out electrochemical deposition operation, the Pb in solution
2+separate out at negative electrode and obtain metallic lead.
(3) CX-EW indirect electrochemical depositing operation
The core technology of CX-EW technique is: Na
2cO
3desulfurization-H
2o
2conversion-H
2bF
4/ H
2siF
4dissolving-electrochemical cathode reduces.CX-EW technique is substantially identical with RSR technique, utilizes Na
2cO
3as sweetening agent, next adopts H
2o
2pbO in reduction lead plaster
2, adopt HBF equally afterwards
4or H
2siF
6solution leaches PbO and PbCO
3obtained electrolytic solution, electrochemical deposition method generates the higher cathode lead of purity.
(4) NaOH-FeSO
4-KNaC
4h
4o
6indirect electrochemical depositing operation
Hunan University have developed the lead plaster hydrometallurgical processes similar to RSR technological line.The core technology of this technique is: FeSO
4transform-NaOH desulfurization-KNaC
4h
4o
6dissolving-electrochemical cathode reduces.Adopt H
2sO
4feSO in solution
4for reductive agent is by PbO
2reduction generates PbSO
4carry out reduction to transform, adopt NaOH afterwards as sweetening agent by PbSO
4be converted into PbO, finally utilize NaOH-KNaC
4h
4o
6dissolve PbO and obtain electrolytic solution, obtain lead by electrochemical deposition method.
2.2.3 the subject matter of electrochemical deposition process existence
Electrochemical deposition method recovery process, solves the SO in lead plaster pyrometallurgical smelting process
2the volatilization problems of metallic lead under discharge and high temperature.But there is following outstanding problem in existing hydrometallurgic recovery treatment process:
(1) PbO on anode
2precipitation problem: although each technique all PbO on minimizing anode
2precipitation aspect done corresponding research, but be also difficult to thoroughly suppress PbO on anode at present
2generation, cause the plumbous rate of recovery low.
(2) consume a large amount of chemical reagent and produce by product problem: it is many that each technique relates to flow process, length consuming time also introduces a large amount of chemical reagent, and a large amount of sulfate by-products is produced in desulfurization conversion process, not only add the preparation cost of Pb, also have impact on economic benefit.
(3) energy expenditure is high, investment is large: because in electrochemical deposition process, only at negative electrode generation effecting reaction, therefore the energy consumption of electrochemical deposition Footwall drift lead is high, prepare 1 kilogram of plumbous energy expenditure and be about 12kWh, even taller than the energy consumption of traditional fire metallurgy process.In addition, adopt electrochemical deposition technique, must use special equipment, plant investment is large, is suitable only for large-scale recovery plant and uses.
For Problems existing in above-mentioned technical process, constantly have developed again following several new technique, economic benefit and environmental benefit have had further improvement.
2.3 wet method lead plaster conversion-pyrogenic processes are prepared plumbous oxide coupling and are recycled splicer's technology
In order to give full play to the advantage of wet method and pyrogenic process recycling Technology, consider the plumbous feature used mainly as lead storage battery lead plaster of recovery, adopting wet method lead plaster conversion-pyrogenic process to prepare plumbous oxide coupling recycling splicer technology is comparatively ideal Technology simultaneously.
2.3.1PbO the importance in the preparation of lead-acid battery electrode material
The technique of traditional with metallic lead is lead-acid battery electrode plate active substance prepared by raw material mainly obtains green plate through molten lead, lead powder manufacture and the operation such as cream, coated plate, by the active substance of the green plate obtained after pickling and regaining after adopting the operations such as electrochemistry changes into changes on pole plate.
As can be seen from this production technique, the lead powder based on PbO produced by metal lead pig, the active substance after lead powder regains and changes into after the multiple working procedure such as changing into cream, coated plate, green plate, pole plate on pole plate.Wherein prepare lead powder by lead pig, again through high energy consumption techniques such as melting-oxidations.The manufacturing technology of lead powder adopts ball milled (Shimadzu method) or vapour phase oxidation process (Ba Dunfa) by lead pig, and being made with PbO by oxidation screening through specific equipment lead-power machine is the lead powder of main component.Due to shot or the mutual friction of lead phase and clash into and produce a large amount of heats in lead-power machine in ball milled, temperature in cylindrical shell is increased, under giving in lead-power machine and inputting the effect of oxygen in the air draught of certain temperature and humidity, there is oxidation and generate PbO in shot or lead surface.Vapour phase oxidation process refers to that the plumbous liquid of melting reacts with the oxygen in air the process making lead powder after gaseous oxidation indoor are stirred mist formation drop-wise.In general control lead powder, PbO massfraction is about 75% (oxidisability also referred to as lead powder).
Lead powder forms the fertile material of battery lead plate active substance as lead storage battery, and the character of lead powder and quality control have material impact for the performance of lead storage battery.Lead storage battery prepared by ultra-fine PbO particle has the advantage such as heavy body and long discharge and recharge life-span, and its shortcoming is that to prepare ultra-fine lead oxide cost too high.In sum, the metal Pb that waste lead accumulator lead plaster reclaims is applied in storage battery production, needs consumed energy again, and just can be prepared into PbO by ball milled or vapour phase oxidation process is the lead powder of main component.
2.3.2 the Technology of PbO is directly prepared in research and development
Tradition scrap lead cream, through the pyrometallurgy of high energy consumption or electrodeposition hydrometallurgical recovery metal Pb, if metal Pb will prepare the active substance of pole plate again for the production of lead storage battery as raw material, has to pass through the complicated production technical process of multiple working procedure.If adopt suitable wet method lead plaster conversion-pyrogenic process to prepare plumbous oxide coupling technique, by the ultra-fine PbO powder of the direct Application and preparation of waste lead accumulator lead plaster in battery production, energy consumption will be reduced, and due to the superfine powder comparatively characteristic such as bigger serface, heavy body, long-life high-performance store battery can be prepared.Typical Technology has:
(1) the Placid technique improved
Pyrogenic process-wet method combined plumbous recovery technology that the Placid technique improved is come by Placid technological development is a kind of process integration of pyrogenic process-wet method.Leach identical with Placid technique with scavenging process, uniquely replace electrochemical deposition method unlike employing lime precipitation.This technique main raw material is lead plaster and inexpensive common lime, and residue is mainly gypsum, its lead content 5%, the Pb (OH) of generation
2also pure lead was originally obtained with hard coal after decomposing in subsequent reactions still.The leaching efficiency of this technique is identical with Placid technique with product purity.In addition, also can utilize sodium carbonate wet desulphurization conversion is carried out to lead plaster after carry out again pyrogenic process lead reclaim, the decomposition temperature of lead plaster is made to be reduced to 358 DEG C after conversion by 800 DEG C before transforming, thus the energy consumption reduced in recycling waste lead batteries process, avoid the discharge of sulfurous gas simultaneously, decrease the pollution to environment.
(2) citric acid hydrometallurgic recovery and the directly ultra-fine PbO powder technique of preparation
Utilize the structure of the stable chelant complex of lead citrate, citric acid is used for the wet recycling process of lead plaster, under the inspiration of this thinking, univ cambridge uk's (CambridgeUniversity) Materials science and Department of Metallurgy have developed a kind of novel process adopting citric acid wet processing waste lead accumulator lead plaster.
The core technology of this technique is: citric acid desulfurization-H
2o
2conversion-lead citrate thermal decomposition process.Lead plaster main component is PbO, PbSO
4and PbO
2, also containing the metal such as a small amount of metal Pb and Sb.Utilize citric acid that above-mentioned 3 kinds of leaded Substance Transformations are become organo-lead compound, concrete reaction equation is as follows:
PbO+C
6H
8O
7·H
2O→Pb(C
6H
6O
7)·H
2O+H
2O
PbO
2+C
6H
8O
7·H
2O+H
2O
2→Pb(C
6H
6O
7)·H
2O+O
2+2H
2O
3PbSO4+2[Na
3C
6H
5O
7·2H
2O]→[3Pb·2(C
6H
5O
7)]·3H
2O+3Na
2SO
4+H
2O
PbO, PbSO
4and PbO
23 kinds of initiators and blending ingredients composition lead plaster and citric acid solution react, all can obtain the white crystal being similar to lead citrate.Under PbO yellow powder and aqueous citric acid solution normal temperature can direct reaction synthesizing citric acid plumbous; PbO
2during black powder and aqueous citric acid solution react, add H simultaneously
2o
2for reductive agent, Pb (IV) is reduced to Pb (II), also can reacts generation lead citrate under normal temperature, release oxygen simultaneously; PbSO
4white powder and aqueous citric acid solution, add trisodium citrate as sweetening agent, also can react and generate lead citrate crystal, synchronously complete desulfurization conversion, simultaneously by-product Na
2sO
4, the Na in filtrate
2sO
4general employing crystallisation by cooling is as byproduct (Na
2sO
410H
2o) reclaim.Filtrate returns original wet processing process, realizes the closed circulation of whole filtrate, avoids the secondary pollution causing discharging of waste liquid.Above-mentioned 3 reactions are carried out for kind of the essential substance of 3 in lead plaster, and operation is easy, the time is short, and lead recovery is all higher than 99%.The lead citrate precipitated product obtained is after further removal of impurities, washing and filtering, through low-temperature bake (300 ~ 500 DEG C), the powder body material that can to obtain with PbO and Pb be main component, can directly as the raw material preparing lead storage battery active substance.
Lead citrate is the Metal-organic complex with macromolecular structure that the atom such as lead and oxygen, carbon, hydrogen is formed.The Nomenclature Composition and Structure of Complexes of the lead citrate generated combines from organic ligand because plumbous and may form different configurations and different ligancies, so may there are differences because of the change of reaction conditions.
By the organic compound of above-mentioned gained lead at relatively low temperature calcination directly can obtain plumbous oxide, and without the generation of the pollutents such as lead steam, lead dust and sulfurous gas in whole process, also to produce without slag.
Citric acid wet processing lead plaster technique has the following advantages compared with traditional pyrometallurgical smelting flow process:
1. eliminate the preparation process of metallic lead, only the organo-lead compound obtained need be carried out low temperature calcination, energy consumption is relatively low, considerably reduces energy consumption.
2. be that raw material carries out low temperature calcination with organo-lead compound, directly prepare PbO powder, directly can use as the lead powder producing lead storage battery, eliminate and prepare PbO powder process with lead.
3. be that raw material carries out low temperature calcination and can obtain ultra-fine PbO powder by organo-lead compound, ultra-fine PbO powder as the active substance of pole plate, for the active substance preparing high performance lead-acid battery electrode provides condition.
4. simplify technical process, decrease unit operation, operation is relatively simple, safe reliability is high.
5. high melt discharge SO is eliminated
2with the atmospheric polluting material of volatility lead dust, improve the plumbous rate of recovery.
6. directly obtain yellow lead oxide in technological process, decrease the plumbous production link to yellow lead oxide in the production engineering of lead storage battery.The lead of existing waste lead accumulator can be utilized to reclaim existing installation, reduce the equipment investment of technological process.
Although this technique is also in the conceptual phase in laboratory now, consider from above several respects, this technique has application and DEVELOPMENT PROSPECT preferably, has great reference to the recycling technology of waste lead accumulator.
Also there is following outstanding problem in this treatment process:
1. a large amount of chemical reagent is consumed: at citric acid desulfurization-H
2o
2in conversion process, consume citric acid, Trisodium Citrate and H
2o
2, the technico-economical comparison of influence process, the use of a large amount of chemical reagent, has increased considerably preparation cost, the economic benefit of influence process.
2. a large amount of sulfate by-products is produced: in desulfurization conversion process, produce a large amount of sulfate by-products, not only add the preparation cost of Pb, affect economic benefit, and open up the Application Areas of these by products and find the major control factors that suitable market product becomes this technology.
3. the price of citric acid, Trisodium Citrate is high, and the atom utilization of this technique is still on the low side.
Therefore, research and develop economic environmental protection, Technology that atom utilization is high, solve Problems existing tool and be of great significance.
Summary of the invention
The invention provides a kind of with waste lead accumulator through pre-treatment obtain containing PbO, PbSO
4, PbO
2lead plaster be raw material, through PbO, PbSO that separation and purification obtains
4, PbO
2, and directly as the raw material preparing lead-acid battery electrode active substance, realize the direct utilization of waste lead accumulator lead plaster.
Realizing above-mentioned purpose technical scheme is:
A kind of PbO, PbSO
4, PbO
2the separation method of mixture, what the lead plaster particularly obtained with the lead-containing material of waste lead accumulator obtained through physical separation method process contains PbO, PbSO
4, PbO
2mixture is raw material, adopts acidleach to dissolve, leaches dissolving, separation and purification, solid-liquid separation coupling technique, realize PbO, PbSO
4, PbO
2the separation of mixture.Step is as follows:
(1) washing impurity-removing: in washing impurity-removing equipment, by PbO, PbSO
4, PbO
2mixture carries out washing impurity-removing and removes soluble impurity, and the material through washing impurity-removing enters next step;
(2) solid-liquid separation: in solid-liquid separation equipment, material obtained in the previous step is carried out solid-liquid separation, the liquid phase material obtained enters the first step and recycles as washings after further removal of impurities process, is separated the solid-phase material obtained and enters next step;
(3) acidleach is dissolved: in leaching dissolution equipment, add Acid leaching agent, with PbO, PbSO
4, PbO
2mixture mixes, and PbO wherein and acid react, and makes the PbO in material generate water-soluble Pb
2+ion enters solution, and the material dissolved through acidleach enters next step;
(4) solid-liquid separation: in solid-liquid separation equipment, material obtained in the previous step is carried out solid-liquid separation, the liquid phase material obtained obtains water-soluble lead salt or processes further obtaining PbO through further separation and purification, and the solid-phase material obtained enters next step;
(5) leaching is dissolved: in leaching dissolution equipment, add leaching agent and PbSO obtained in the previous step
4and PbO
2mixture, PbSO wherein
4enter leaching liquid, the material dissolved through leaching enters next step;
(6) in solid-liquid separation equipment, material obtained in the previous step is carried out solid-liquid separation, the liquid phase material obtained enters the further separation and purification of the tenth step, and solid-phase material enters the further separation and purification of the 13 step;
(7) removal of impurities decolouring: in removal of impurities decolorizing and refining equipment, add adsorption-edulcoration agent, the liquid phase material that the 4th step obtains is carried out removal of impurities decolouring, what decolour through adsorption-edulcoration contains Pb
2+solution enters next step;
(8) solid-liquid separation: in solid-liquid separation equipment, material obtained in the previous step is carried out solid-liquid separation, the liquid phase material obtained enters the further separation and purification of the 9th step, and solid-phase material enters previous step after treatment and realizes recycling as adsorption-edulcoration agent;
(9) crystallisation by cooling: in cooling crystallizing equipment, by obtained in the previous step containing Pb
2+refined soln cools, Pb
2+salt-pepper noise is separated out, and obtains Pb through solid-liquid separation
2+product salt, the separation mother liquor obtained enters the 3rd step and uses as the agent of preparation nitrate leaching after further separation, impurity removal;
(10) removal of impurities decolouring: in removal of impurities decolorizing and refining equipment, add adsorption-edulcoration agent, the liquid phase material that the 6th step obtains is carried out removal of impurities decolouring, through the PbSO of adsorption-edulcoration
4solution enters next step;
(11) solid-liquid separation: in solid-liquid separation equipment, material obtained in the previous step is carried out solid-liquid separation, the liquid phase material obtained enters the further separation and purification of the 12 step, and solid-phase material enters previous step after treatment and realizes recycling as adsorption-edulcoration agent;
(12) evaporative crystallization: in evaporation crystallization equipment, material obtained in the previous step is carried out heat, decompression operation, evaporate the solvent removed in solution and enter gas phase, enter vapor phase solvent and enter the 5th step and realize recycling as leaching liquid, while evaporative crystallization, PbSO
4crystallization, through solid-liquid separation, the liquid phase material obtained enters the 5th step and realizes recycling as leaching liquid, and solid-phase material is PbSO
4product;
(13) washing impurity-removing: in washing impurity-removing equipment, add washings, carries out washing impurity-removing separation (washing, extraction, the dissolving removal of impurity) by the solid-phase material that the 6th step obtains;
(14) solid-liquid separation: in solid-liquid separation equipment, material obtained in the previous step is carried out solid-liquid separation, the liquid phase material obtained enters the 13 step and realizes recycling as washings after further separation and purification, and the solid-phase material obtained enters next step;
(15) drying and roasting: solid-phase material obtained in the previous step is carried out drying, roasting removing impurity, the solid-phase material obtained is PbO
2product.
Further, the acid described in the 3rd step acidleach dissolution process is any one in nitric acid, acetic acid, citric acid, hexafluorosilicic acid, trifluoromethane sulfonic acid.
Further, the 5th step leaching liquid NH
3h
2o-(NH
4)
2sO
4or C
6h
8o
7h
2o-Na
3c
6h
5o
72H
2o or (NH
4)
2siF
6-H
2siF
6any one.
Further, the 7th step removal of impurities decolouring and the removal of impurities discoloring agent described in the tenth step removal of impurities decolorization are activated carbon, diatomite and adsorbent of molecular sieve, and also can be the mixture of wherein two components or three components, consumption be the 1.0%-5.0% of solution quality.
Further, the 9th step crystallisation by cooling temperature is 0 DEG C-20 DEG C, and working pressure is for be usually pressed onto 10.0MPa.
Further, the absolute pressure of the 12 step evaporation deamination decompression operation is 0.01MPa-0.08Ma, and service temperature is at 20 DEG C-80 DEG C.
Further, PbO, PbSO in second step washing separation
4, PbO
2the mass ratio of mixture and water is 1:1-1:10.
Further, the washing impurity-removing liquid described in the 13 step washing impurity-removing process is water, methyl alcohol, ethanol, also can be the mixture of wherein two components or three components, and total add-on of described washing impurity-removing liquid and the mass ratio of plumbic oxide are 1:1-1:10.
Further, in the 15 step drying and roasting process, drying temperature is 20 DEG C-200 DEG C, and maturing temperature is 200 DEG C-600 DEG C.
Further, the washing impurity-removing liquid described in the first step washing impurity-removing process is water, methyl alcohol, ethanol, also can be the mixture of wherein arbitrarily component, and total add-on of described washing impurity-removing liquid is the mass ratio of solid-phase material and washing impurity-removing liquid is 1:1-1:10.
The technical thought of the inventive method is as follows:
(1) first, utilize PbO easily and acid-respons, the product of generation is soluble in the characteristic of water, and take acid as leaching agent, PbO and acid react and generates water-soluble Pb
2+salt, by lead plaster mixture (PbO, PbSO
4, PbO
2) in PbO leach in acid solution, reclaim water-soluble Pb
2+salt, as the raw material of other lead compounds of preparation.
(2) secondly, NH is adopted
3h
2o-(NH
4)
2sO
4or C
6h
8o
7h
2o-Na
3c
6h
5o
72H
2o or (NH
4)
2siF
6-H
2siF
6for leaching agent, utilize PbSO
4the feature that solubleness in leaching agent increases with the rising of concentration and temperature, in leaching process, adopts the leaching agent of high density to make PbSO
4transfer to liquid phase from solid phase, the PbSO obtained
4solution can removal of impurities process further, is met the electrolytic solution of electrochemical method process, through the PbSO of separation and purification
4solution can adopt the de-NH of evaporation
3method, reduce NH in leaching agent
3concentration, make PbSO
4crystallization, obtains the PbSO refined
4product, as electrochemical production PbO
2with the raw material of Pb.
(3) the 3rd, take into full account PbO
2difficulty reacts and there is the characteristic of suitable solvent, exists, to reduce the treating processes of material in sepn process with solid.Through being separated leaching PbO and PbSO
4process, further removal of impurities, obtains the PbO refined
2material.
The main technical principle that the present invention adopts:
(1) make use of the singularity of waste lead accumulator lead plaster: the product that waste lead accumulator lead plaster mainly battery lead plate transforms after the long-term discharge and recharge of active substance.Lead plaster main component is PbO, PbSO
4and PbO
2, also containing the metal such as a small amount of metal Pb and Sb, wherein PbSO
4up to more than 50%.Adopt suitable separation and refining method to carry out separation and can obtain lead-containing compounds (PbO, PbSO
4and PbO
2), these lead-containing compounds, directly as the raw material preparing lead-acid battery electrode, are most economical, the effective Application way of waste lead accumulator lead plaster, particularly the most effective means of raising atom economy utilization ratio.
(2) make use of the singularity of the principle of work of lead storage battery: after lead storage battery electric discharge, two electrode active materials are all converted into the lead sulfate of indissoluble.In process of charging, change PbO at anode lead sulfate
2, change Pb at negative electrode lead sulfate.Therefore, PbSO
4, PbO
2with main composition and existence form that Pb is lead-acid battery electrode active substance.
(3) make use of the singularity of lead-acid battery electrode active substance in preparation process: the technique of traditional with metallic lead is lead-acid battery electrode plate active substance prepared by raw material obtains green plate primarily of molten lead, lead powder manufacture and the unit operation such as cream, coated plate, regains the active substance that change into rear pole plate on after adopting the operations such as electrochemistry changes into by the green plate obtained.Wherein PbO is the important intermediate in electrode active material preparation process.
(4) PbSO is utilized
4be soluble in the characteristic of compound electrolyte solution: PbSO
4dissolve in following three kind solvents:
①NH
3·H
2O-(NH
4)
2SO
4
②C
6H
8O
7·H
2O-Na
3C
6H
5O
7·2H
2O
③PbSiF
6-H
2SiF
6
Therefore, select suitable solvent systems, can by PbSO
4transfer to liquid phase from solid phase, transform thoroughly, efficiency is high.
(5) PbO is considered
2difficulty reacts and there is the characteristic of suitable solvent: taken into full account PbO
2difficulty reacts and there is the characteristic of suitable solvent, still exists with solid, to reduce material treating processes in sepn process.Lead sulfate is insoluble in water, and its solubleness is 0.0041g/100g water (20 DEG C).Lead sulfate is dissolved in rare strong acid solution hardly, but can be dissolved in denseer sulphuric acid soln, ammonium acetate solution and strong base solution, generates lyotrope matter.Take into full account PbO
2difficulty reacts and there is the characteristic of suitable solvent, still exists with solid, to reduce material treating processes in sepn process.Through being separated leaching PbO and PbSO
4process, further removal of impurities process, obtains at refining PbO
2material, can directly as PbO
2product material uses.
Beneficial effect of the present invention is embodied in: what the present invention obtained through pre-treatment with waste lead accumulator contains PbO, PbSO
4, PbO
2lead plaster be raw material, through PbO, PbSO that separation and purification obtains
4, PbO
2product.PbO, PbSO of obtaining
4, PbO
2product, directly as the raw material preparing lead-acid battery electrode active substance, is changed into by electrochemistry in sulphuric acid soln, obtains PbO respectively at anode and negative electrode
2with Pb active substance, realizing the direct utilization of waste lead accumulator lead plaster, is the processing method of the waste lead accumulator lead resourceization recycling that a kind of technique is simple, production cost is low, by product is few, atom utilization is high.
Accompanying drawing explanation
Fig. 1 is process flow sheet of the present invention.
Embodiment
Major process unit is: washing impurity-removing equipment, leaching dissolution equipment, solid-liquid separation equipment etc.
Below in conjunction with drawings and Examples, the present invention is further detailed explanation.
Embodiment one
As shown in Figure 1, a kind of PbO, PbSO
4, PbO
2the separation method of mixture, particularly with PbO, PbSO that the lead-containing material process of waste lead accumulator obtains through physical separation method
4, PbO
2the lead plaster of mixture is raw material, adopts acidleach to dissolve, leaches dissolving, separation and purification, solid-liquid separation coupling technique, realize PbO, PbSO
4, PbO
2the separation of mixture.It is characterized in that described method steps is as follows:
(1) washing impurity-removing: in autoclave agitator treating impurity removing equipment, by PbO, PbSO
4, PbO
2mixture carries out washing impurity-removing and removes soluble impurity, and washing impurity-removing liquid used in washing impurity-removing process is water, and the add-on of water is the mass ratio of solid-phase material and washing impurity-removing liquid is 1:1, and the material through washing impurity-removing enters next step;
(2) solid-liquid separation: in decanter type solid-liquid separation device, material obtained in the previous step is carried out solid-liquid separation, the liquid phase material obtained enters the first step and recycles as washings after further removal of impurities process, is separated the solid-phase material obtained and enters next step;
(3) acidleach is dissolved: in autoclave leaching dissolution equipment, add Acid leaching agent nitric acid, concentration of nitric acid is 1.0mol/L, nitric acid dosage and PbO, PbSO
4and PbO
2be 1.0:1.2 with the mol ratio of PbO in mixture, service temperature is 20 DEG C, and the PbO in material and acid react, and makes the PbO in material generate water-soluble Pb
2+ion enters solution, and the material dissolved through acidleach enters next step;
(4) solid-liquid separation: in decanter type solid-liquid separation device, material obtained in the previous step is carried out solid-liquid separation, the liquid phase material obtained obtains water-soluble lead salt or processes further preparing PbO through further separation and purification, and the solid-phase material obtained enters next step;
(5) leaching is dissolved: in tubular type leaching dissolution equipment, adding leaching agent is NH
3h
2o-(NH
4)
2sO
4, leaching liquid NH
3h
2o-(NH
4)
2sO
4free ammonia volumetric molar concentration is 36.0mol/L, and in solution, ammonium sulfate volumetric molar concentration concentration is 6.0mol/L, and service temperature is 20 DEG C, and the material dissolved through leaching enters next step;
(6) in centrifugal solid-liquid separation equipment, material obtained in the previous step is carried out solid-liquid separation, the liquid phase material obtained enters the further separation and purification of the tenth step, and solid-phase material enters the further separation and purification of the 13 step;
(7) removal of impurities decolouring: stir in removal of impurities decolorizing and refining equipment in autoclave, add activated carbon, the consumption of activated carbon is 1.0% of solution quality, and the liquid phase material that the 4th step obtains is carried out removal of impurities decolorization operations, what decolour through adsorption-edulcoration contains Pb
2+solution enters next step;
(8) solid-liquid separation: in any one solid-liquid separation equipment in decanter type solid-liquid separation device, material obtained in the previous step is carried out solid-liquid separation, the liquid phase material obtained enters the further separation and purification of the 9th step, and solid-phase material enters previous step after treatment and realizes recycling as adsorption-edulcoration agent;
(9) crystallisation by cooling: in autoclave stirred type crystallizer equipment, by obtained in the previous step containing Pb
2+refined soln is cooled to 0 DEG C, Pb
2+salt-pepper noise is separated out, and obtains Pb through solid-liquid separation
2+product salt, the separation mother liquor obtained enters the liquid use of the 3rd step as the leaching of configuration acid solution after further separation, impurity removal;
(10) removal of impurities decolouring: in removal of impurities decolorizing and refining equipment, add adsorption-edulcoration agent activated carbon, activated carbon content is 5.0% of solution quality, and the liquid phase material that the 6th step obtains is carried out removal of impurities decolorization operations, through the PbSO of adsorption-edulcoration
4solution enters next step;
(11) solid-liquid separation: in decanter type solid-liquid separation device, material obtained in the previous step is carried out solid-liquid separation, the liquid phase material obtained enters the further separation and purification of the 12 step, and solid-phase material enters previous step after treatment and realizes recycling as adsorption-edulcoration agent;
(12) evaporative crystallization: stir in evaporation crystallization equipment in autoclave, material obtained in the previous step is carried out heat, decompression operation, the absolute pressure of evaporation deamination decompression operation is 0.01MPa, evaporate the solvent removed in solution and enter gas phase, enter vapor phase solvent enter the 5th step as leaching liquid realize recycle, while evaporative crystallization, PbSO
4crystallization, through solid-liquid separation, the liquid phase material obtained enters the 5th step and realizes recycling as leaching liquid, and solid-phase material is PbSO
4product;
(13) washing impurity-removing: in washing impurity-removing equipment, adds washings water, and the consumption of water is the mass ratio of solid-phase material plumbic oxide quality and washing impurity-removing liquid is 1:10;
(14) solid-liquid separation: in centrifugal solid-liquid separation device, material obtained in the previous step is carried out solid-liquid separation, the liquid phase material obtained enters the 13 step and realizes recycling as washings after further separation and purification, and solid-phase material enters next step;
(15) drying and roasting: solid-phase material obtained in the previous step is carried out drying, drying temperature is 200 DEG C, and maturing temperature is 600 DEG C.Roasting removing impurity, the solid-phase material obtained is PbO
2product.
Embodiment two
As shown in Figure 1, a kind of PbO, PbSO
4, PbO
2the separation method of mixture, particularly with PbO, PbSO that the lead-containing material process of waste lead accumulator obtains through physical separation method
4, PbO
2the lead plaster of mixture is raw material, adopts acidleach to dissolve, leaches dissolving, separation and purification, solid-liquid separation coupling technique, realize PbO, PbSO
4, PbO
2the separation of mixture.It is characterized in that described method steps is as follows:
(1) washing impurity-removing: in tubular type washer washing impurity-removing equipment, by PbO, PbSO
4, PbO
2mixture carries out washing impurity-removing and removes soluble impurity, washing impurity-removing liquid used in washing impurity-removing process is methyl alcohol, total add-on of described washing impurity-removing liquid is the mass ratio of solid-phase material and washing impurity-removing liquid is 1:1, and the material through washing impurity-removing enters next step;
(2) solid-liquid separation: in vane-type solid-liquid separation device, material obtained in the previous step is carried out solid-liquid separation, the liquid phase material obtained enters the first step and recycles as washings after further removal of impurities process, is separated the solid-phase material obtained and enters next step;
(3) acidleach is dissolved: in tubular type leaching dissolution equipment, add Acid leaching agent acetic acid, acetic acid concentration is 8.0mol/L, sour consumption and PbO, PbSO
4and PbO
2be 1.0:2.0 with the mol ratio of PbO in mixture, service temperature is 40 DEG C, and the PbO in material and acid react, and makes the PbO in material generate water-soluble Pb
2+ion enters solution, and the material dissolved through acidleach enters next step;
(4) solid-liquid separation: in press filter type solid-liquid separation device, material obtained in the previous step is carried out solid-liquid separation, the liquid phase material obtained obtains water-soluble lead salt or processes further preparing PbO through further separation and purification, and solid-phase material enters next step;
(5) leaching is dissolved: leach in static mixer in dissolution equipment, adding leaching agent leaching liquid is C
6h
8o
7h
2o-Na
3c
6h
5o
72H
2o, leaching liquid NH
3c
6h
8o
7h
2the concentration of O is 6.0mol/L, Na in solution
3c
6h
5o
7volumetric molar concentration concentration is 4.0mol/L, and the material dissolved through leaching enters next step;
(6) in centrifugal solid-liquid separation device, material obtained in the previous step is carried out solid-liquid separation, the liquid phase material obtained enters the further separation and purification of the tenth step, and solid-phase material enters the further separation and purification of the 13 step;
(7) removal of impurities decolouring: in static mixing removal of impurities decolorizing and refining equipment, add adsorption-edulcoration agent diatomite and adsorbent of molecular sieve, consumption is 3.0% of solution quality, and the liquid phase material that the 4th step obtains is carried out removal of impurities decolorization operations, and what decolour through adsorption-edulcoration contains Pb
2+solution enters next step;
(8) solid-liquid separation: in press filter type-liquid separating apparatus, material obtained in the previous step is carried out solid-liquid separation, the liquid phase material obtained enters the further separation and purification of the 9th step, and solid-phase material enters previous step after treatment and realizes recycling as adsorption-edulcoration agent;
(9) crystallisation by cooling: in static mixing cooling crystallizing equipment, by obtained in the previous step containing Pb
2+refined soln is cooled to 20 DEG C, Pb
2+salt-pepper noise is separated out, and obtains Pb through solid-liquid separation
2+product salt, the separation mother liquor obtained enters the liquid use of the 3rd step as the leaching of configuration acid solution after further separation, impurity removal;
(10) removal of impurities decolouring: in removal of impurities decolorizing and refining equipment, add adsorption-edulcoration agent molecule sieve adsorbant, molecular sieve consumption is 1.0% of solution quality, and the liquid phase material that the 6th step obtains is carried out removal of impurities decolorization operations, through the PbSO of adsorption-edulcoration
4solution enters next step;
(11) solid-liquid separation: in vane-type solid-liquid separation device, material obtained in the previous step is carried out solid-liquid separation, the liquid phase material obtained enters the further separation and purification of the 12 step, and solid-phase material enters previous step after treatment and realizes recycling as adsorption-edulcoration agent;
(12) evaporative crystallization: in static mixer in evaporation crystallization equipment, material obtained in the previous step is carried out heat, decompression operation, the absolute pressure of evaporation deamination decompression operation is 0.08Ma, evaporate the solvent removed in solution and enter gas phase, enter vapor phase solvent enter the 5th step as leaching liquid realize recycle, while evaporative crystallization, PbSO
4crystallization, through solid-liquid separation, the liquid phase material obtained enters the 5th step and realizes recycling as leaching liquid, and solid-phase material is PbSO
4product;
(13) washing impurity-removing: in washing impurity-removing equipment, adds washings methyl alcohol, and the mass ratio of methyl alcohol add-on and plumbic oxide is 1:1;
(14) solid-liquid separation: in decanter type solid-liquid separation device, material obtained in the previous step is carried out solid-liquid separation, the liquid phase material obtained enters the 13 step and realizes recycling as washings after further separation and purification, and solid-phase material enters next step;
(15) drying and roasting: solid-phase material obtained in the previous step is carried out drying, drying temperature is 80 DEG C, and maturing temperature is 200 DEG C.Roasting removing impurity, the solid-phase material obtained is PbO
2product.
Embodiment three
As shown in Figure 1, a kind of PbO, PbSO
4, PbO
2the separation method of mixture, particularly with PbO, PbSO that the lead-containing material process of waste lead accumulator obtains through physical separation method
4, PbO
2the lead plaster of mixture is raw material, adopts acidleach to dissolve, leaches dissolving, separation and purification, solid-liquid separation coupling technique, realize PbO, PbSO
4, PbO
2the separation of mixture.It is characterized in that described method steps is as follows:
(1) washing impurity-removing: in static mixing washing impurity-removing equipment, by PbO, PbSO
4, PbO
2mixture carries out washing impurity-removing and removes soluble impurity, washing impurity-removing liquid used in washing impurity-removing process is ethanol, total add-on of described washing impurity-removing liquid is the mass ratio of solid-phase material and washing impurity-removing liquid is 1:10, and the material through washing impurity-removing enters next step;
(2) solid-liquid separation: in press filter type solid-liquid separation device, material obtained in the previous step is carried out solid-liquid separation, the liquid phase material obtained enters the first step and recycles as washings after further removal of impurities process, is separated solid-phase material and enters next step;
(3) acidleach is dissolved: stir in leaching dissolution equipment in autoclave, add Acid leaching agent citric acid, acid concentration is 4.0mol/L, sour consumption and PbO, PbSO
4and PbO
2be 1.0:2.0 with the mol ratio of PbO in mixture, service temperature is 60 DEG C, and the PbO in material and acid react, and makes the PbO in material generate water-soluble Pb
2+ion enters solution, and the material dissolved through acidleach enters next step;
(4) solid-liquid separation: in centrifugal solid-liquid separation device, material obtained in the previous step is carried out solid-liquid separation, the liquid phase material obtained obtains water-soluble lead salt or processes further preparing PbO through further separation and purification, and solid-phase material enters next step;
(5) leaching is dissolved: in tubular type leaching dissolution equipment, adding leaching agent leaching liquid is C
6h
8o
7h
2o-Na
3c
6h
5o
72H
2o, leaching liquid C
6h
8o
7volumetric molar concentration be 6.0mol/L, Na in solution
3c
6h
5o
7volumetric molar concentration concentration be 6.0mol/L, service temperature is 60 DEG C, through leaching dissolve material enter next step;
(6) in decanter type solid-liquid separation device, material obtained in the previous step is carried out solid-liquid separation, the liquid phase material obtained enters the further separation and purification of the tenth step, and solid-phase material enters the further separation and purification of the 13 step;
(7) removal of impurities decolouring: stir in removal of impurities decolorizing and refining equipment in autoclave, add adsorption-edulcoration agent activated carbon, diatomite and molecular sieve, its consumption is 3.0% of solution quality, and the liquid phase material that the 4th step obtains is carried out removal of impurities decolorization operations, and what decolour through adsorption-edulcoration contains Pb
2+solution enters next step;
(8) solid-liquid separation: in vane-type solid-liquid separation device, material obtained in the previous step is carried out solid-liquid separation, the liquid phase material obtained enters the further separation and purification of the 9th step, and solid-phase material enters previous step after treatment and realizes recycling as adsorption-edulcoration agent;
(9) crystallisation by cooling: in autoclave stirred type crystallizer equipment, by obtained in the previous step containing Pb
2+refined soln is cooled to 0 DEG C, Pb
2+salt-pepper noise is separated out, and obtains Pb through solid-liquid separation
2+product salt, the separation mother liquor obtained enters the liquid use of the 3rd step as the leaching of configuration acid solution after further separation, impurity removal;
(10) removal of impurities decolouring: in removal of impurities decolorizing and refining equipment, adding adsorption-edulcoration agent is activated carbon, diatomite and adsorbent of molecular sieve, its consumption is 2.0% of solution quality, and the liquid phase material that the 6th step obtains is carried out removal of impurities decolorization operations, through the PbSO of adsorption-edulcoration
4solution enters next step;
(11) solid-liquid separation: in decanter type solid-liquid separation device, material obtained in the previous step is carried out solid-liquid separation, the liquid phase material obtained enters the further separation and purification of the 12 step, and solid-phase material enters previous step after treatment and realizes recycling as adsorption-edulcoration agent;
(12) evaporative crystallization: stir in evaporation crystallization equipment in autoclave, material obtained in the previous step is carried out heat, decompression operation, the absolute pressure of evaporation deamination decompression operation is 0.04Ma, evaporate the solvent removed in solution and enter gas phase, enter vapor phase solvent enter the 5th step as leaching liquid realize recycle, while evaporative crystallization, PbSO
4crystallization, through solid-liquid separation, the liquid phase material obtained enters the 5th step and realizes recycling as leaching liquid, and solid-phase material is PbSO
4product;
(13) washing impurity-removing: in washing impurity-removing equipment, adding washings is water, methyl alcohol and ethanol, and total add-on of washing impurity-removing liquid and the mass ratio of plumbic oxide are 1:5;
(14) solid-liquid separation: in vane-type solid-liquid separation device, material obtained in the previous step is carried out solid-liquid separation, the liquid phase material obtained enters the 13 step and realizes recycling as washings after further separation and purification, and solid-phase material enters next step;
(15) drying and roasting: solid-phase material obtained in the previous step is carried out drying, drying temperature is 120 DEG C, and maturing temperature is 300 DEG C.Roasting removing impurity, the solid-phase material obtained is PbO
2product.
Embodiment four
As shown in Figure 1, a kind of PbO, PbSO
4, PbO
2the separation method of mixture, particularly with PbO, PbSO that the lead-containing material process of waste lead accumulator obtains through physical separation method
4, PbO
2the lead plaster of mixture is raw material, adopts acidleach to dissolve, leaches dissolving, separation and purification, solid-liquid separation coupling technique, realize PbO, PbSO
4, PbO
2the separation of mixture.It is characterized in that described method steps is as follows:
(1) washing impurity-removing: in static mixing washer in washing impurity-removing equipment, by PbO, PbSO
4, PbO
2mixture carries out washing impurity-removing and removes soluble impurity, washing impurity-removing liquid used in washing impurity-removing process is water, methyl alcohol and ethanol, total add-on of washing impurity-removing liquid is the mass ratio of solid-phase material and washing impurity-removing liquid is 1:4, and the material through washing impurity-removing enters next step;
(2) solid-liquid separation: in decanter type solid-liquid separation device, material obtained in the previous step is carried out solid-liquid separation, the liquid phase material obtained enters the first step and recycles as washings after further removal of impurities process, is separated the solid-phase material obtained and enters next step;
(3) acidleach is dissolved: in autoclave stirred type crystallizer leaching dissolution equipment, add Acid leaching agent hexafluorosilicic acid, acid concentration is 8.0mol/L, sour consumption and PbO, PbSO
4and PbO
2be 1.0:1.2 with the mol ratio of PbO in mixture, service temperature is 60 DEG C, and the PbO in material and acid react, and makes the PbO in material generate water-soluble Pb
2+ion enters solution, and the material dissolved through acidleach enters next step;
(4) solid-liquid separation: in decanter type solid-liquid separation device, material obtained in the previous step is carried out solid-liquid separation, the liquid phase material obtained obtains water-soluble lead salt or processes further preparing PbO through further separation and purification, and solid-phase material enters next step;
(5) leaching is dissolved: in tubular type leaching dissolution equipment, add leaching agent leaching liquid (NH
4)
2siF
6-H
2siF
6, the material dissolved through leaching enters next step;
(6) in decanter type solid-liquid separation device, material obtained in the previous step is carried out solid-liquid separation, the liquid phase material obtained enters the further separation and purification of the tenth step, and solid-phase material enters the further separation and purification of the 13 step;
(7) removal of impurities decolouring: stir in removal of impurities decolorizing and refining equipment in autoclave, add adsorption-edulcoration agent activated carbon, activated carbon content is 2.0% of solution quality, and the liquid phase material that the 4th step obtains is carried out removal of impurities decolorization operations, what decolour through adsorption-edulcoration contains Pb
2+solution enters next step;
(8) solid-liquid separation: in press filter type solid-liquid separation device, material obtained in the previous step is carried out solid-liquid separation, the liquid phase material obtained enters the further separation and purification of the 9th step, and solid-phase material enters previous step after treatment and realizes recycling as adsorption-edulcoration agent;
(9) crystallisation by cooling: stir in cooling crystallizing equipment in autoclave, by obtained in the previous step containing Pb
2+refined soln is cooled to 20 DEG C, Pb
2+salt-pepper noise is separated out, and obtains Pb through solid-liquid separation
2+product salt, the separation mother liquor obtained enters the liquid use of the 3rd step as the leaching of configuration acid solution after further separation, impurity removal;
(10) removal of impurities decolouring: in removal of impurities decolorizing and refining equipment, add adsorption-edulcoration agent diatomite and adsorbent of molecular sieve, diatomite and adsorbent of molecular sieve consumption are 2.0% of solution quality, and the liquid phase material that the 6th step obtains is carried out removal of impurities decolorization operations, through the PbSO of adsorption-edulcoration
4solution enters next step;
(11) solid-liquid separation: in vane-type solid-liquid separation device, material obtained in the previous step is carried out solid-liquid separation, the liquid phase material obtained enters the further separation and purification of the 12 step, and solid-phase material enters previous step after treatment and realizes recycling as adsorption-edulcoration agent;
(12) evaporative crystallization: stir in evaporation crystallization equipment in autoclave, material obtained in the previous step is carried out heat, decompression operation, the absolute pressure of evaporation deamination decompression operation is 0.01MPa, evaporate the solvent removed in solution and enter gas phase, enter vapor phase solvent enter the 5th step as leaching liquid realize recycle, while evaporative crystallization, PbSO
4crystallization, through solid-liquid separation, the liquid phase material obtained enters the 5th step and realizes recycling as leaching liquid, and solid-phase material is PbSO
4product;
(13) washing impurity-removing: in washing impurity-removing equipment, adding washings washing impurity-removing liquid is water, methyl alcohol, ethanol, and total add-on of washing impurity-removing liquid and the mass ratio of plumbic oxide are 1:4;
(14) solid-liquid separation: in press filter type solid-liquid separation device, material obtained in the previous step is carried out solid-liquid separation, the liquid phase material obtained enters the 13 step and realizes recycling as washings after further separation and purification, and the solid-phase material obtained enters next step;
(15) drying and roasting: solid-phase material obtained in the previous step is carried out drying, drying temperature is 80 DEG C, and maturing temperature is 320 DEG C.Roasting removing impurity, the solid-phase material obtained is PbO
2product.
Embodiment five
As shown in Figure 1, a kind of PbO, PbSO
4, PbO
2the separation method of mixture, particularly with PbO, PbSO that the lead-containing material process of waste lead accumulator obtains through physical separation method
4, PbO
2the lead plaster of mixture is raw material, adopts acidleach to dissolve, leaches dissolving, separation and purification, solid-liquid separation coupling technique, realize PbO, PbSO
4, PbO
2the separation of mixture.It is characterized in that described method steps is as follows:
(1) washing impurity-removing: in autoclave agitator treating device washing impurity-removing equipment, by PbO, PbSO
4, PbO
2mixture carries out washing impurity-removing and removes soluble impurity, and washing impurity-removing liquid used in washing impurity-removing process is water, and water add-on is the mass ratio of solid-phase material and washing impurity-removing liquid is 1:8, and the material through washing impurity-removing enters next step;
(2) solid-liquid separation: in decanter type solid-liquid separation device, material obtained in the previous step is carried out solid-liquid separation, the liquid phase material obtained enters the first step and recycles as washings after further removal of impurities process, is separated the solid-phase material obtained and enters next step;
(3) acidleach is dissolved: stir in leaching dissolution equipment in autoclave, add Acid leaching agent trifluoromethane sulfonic acid, acid concentration is 8.0mol/L, sour consumption and PbO, PbSO
4and PbO
2be 1.0:1.6 with the mol ratio of PbO in mixture, service temperature is 20 DEG C DEG C, and the PbO in material and acid react, and makes the PbO in material generate water-soluble Pb
2+ion enters solution, and the material dissolved through acidleach enters next step;
(4) solid-liquid separation: in vane-type solid-liquid separation device, material obtained in the previous step is carried out solid-liquid separation, the liquid phase material obtained obtains water-soluble lead salt or processes further preparing PbO through further separation and purification, and solid-phase material enters next step;
(5) leaching is dissolved: stir in leaching dissolution equipment in autoclave, add leaching agent leaching liquid (NH
4)
2siF
6-H
2siF
6, the material dissolved through leaching enters next step;
(6) in press filter type solid-liquid separation device, material obtained in the previous step is carried out solid-liquid separation, the liquid phase material obtained enters the further separation and purification of the tenth step, and solid-phase material enters the further separation and purification of the 13 step;
(7) removal of impurities decolouring: stir in removal of impurities decolorizing and refining equipment in autoclave, add adsorption-edulcoration agent molecule sieve adsorbant, molecular sieve consumption is 1.0% of solution quality, and the liquid phase material that the 4th step obtains is carried out removal of impurities decolorization operations, and what decolour through adsorption-edulcoration contains Pb
2+solution enters next step;
(8) solid-liquid separation: in press filter type solid-liquid separation device, material obtained in the previous step is carried out solid-liquid separation, the liquid phase material obtained enters the further separation and purification of the 9th step, and solid-phase material enters previous step after treatment and realizes recycling as adsorption-edulcoration agent;
(9) crystallisation by cooling: stir in cooling crystallizing equipment in autoclave, by obtained in the previous step containing Pb
2+refined soln is cooled to 20 DEG C, Pb
2+salt-pepper noise is separated out, and obtains Pb through solid-liquid separation
2+product salt, the separation mother liquor obtained enters the liquid use of the 3rd step as the leaching of configuration acid solution after further separation, impurity removal;
(10) removal of impurities decolouring: in removal of impurities decolorizing and refining equipment, add adsorption-edulcoration agent sorbent material, molecular sieve consumption is 1.0%% of solution quality, and the liquid phase material that the 6th step obtains is carried out removal of impurities decolorization operations, through the PbSO of adsorption-edulcoration
4solution enters next step;
(11) solid-liquid separation: in vane-type solid-liquid separation device, material obtained in the previous step is carried out solid-liquid separation, the liquid phase material obtained enters the further separation and purification of the 12 step, and solid-phase material enters previous step after treatment and realizes recycling as adsorption-edulcoration agent;
(12) evaporative crystallization: stir in evaporation crystallization equipment in autoclave, material obtained in the previous step is carried out heat, decompression operation, the absolute pressure of operation is 0.01MPa, evaporate the solvent removed in solution and enter gas phase, enter vapor phase solvent enter the 5th step as leaching liquid realize recycle, while evaporative crystallization, PbSO
4crystallization, through solid-liquid separation, the liquid phase material obtained enters the 5th step and realizes recycling as leaching liquid, and solid-phase material is PbSO
4product;
(13) washing impurity-removing: in washing impurity-removing equipment, add washings, the solid-phase material that 6th step obtains is carried out washing impurity-removing separation, and the washing impurity-removing liquid described in washing impurity-removing process is water, and the mass ratio of water add-on and plumbic oxide is 1:1-1:10;
(14) solid-liquid separation: in any one solid-liquid separation equipment in centrifugal solid-liquid separation device, material obtained in the previous step is carried out solid-liquid separation, the liquid phase material obtained enters the 13 step and realizes recycling as washings after further separation and purification, and solid-phase material enters next step;
(15) drying and roasting: solid-phase material obtained in the previous step is carried out drying, drying temperature is 200 DEG C, and maturing temperature is 600 DEG C.Roasting removing impurity, the solid-phase material obtained is PbO
2product.
Embodiment six
As shown in Figure 1, a kind of PbO, PbSO
4, PbO
2the separation method of mixture, particularly with PbO, PbSO that the lead-containing material process of waste lead accumulator obtains through physical separation method
4, PbO
2the lead plaster of mixture is raw material, adopts acidleach to dissolve, leaches dissolving, separation and purification, solid-liquid separation coupling technique, realize PbO, PbSO
4, PbO
2the separation of mixture.It is characterized in that described method steps is as follows:
(1) washing impurity-removing: in autoclave agitator treating impurity removing equipment, by PbO, PbSO
4, PbO
2mixture carries out washing impurity-removing and removes soluble impurity, and washing impurity-removing liquid used in washing impurity-removing process is water, and water add-on is the mass ratio of solid-phase material and washing impurity-removing liquid is 1:1-1:10, and the material through washing impurity-removing enters next step;
(2) solid-liquid separation: in decanter type solid-liquid separation device, material obtained in the previous step is carried out solid-liquid separation, the liquid phase material obtained enters the first step and recycles as washings after further removal of impurities process, is separated the solid-phase material obtained and enters next step;
(3) acidleach is dissolved: in autoclave leaching dissolution equipment, add Acid leaching agent trifluoromethane sulfonic acid, acid concentration is 8.0mol/L, sour consumption and PbO, PbSO
4and PbO
2be 1.0:2.0 with the mol ratio of PbO in mixture, 60 DEG C, the PbO in material and acid react, and make the PbO in material generate water-soluble Pb
2+ion enters solution, and the material dissolved through acidleach enters next step;
(4) solid-liquid separation: in decanter type solid-liquid separation device, material obtained in the previous step is carried out solid-liquid separation, the liquid phase material obtained obtains water-soluble lead salt or processes further preparing PbO through further separation and purification, and solid-phase material enters next step;
(5) leaching is dissolved: stir in leaching dissolution equipment in autoclave, adding leaching agent leaching liquid is NH
3h
2o-(NH
4)
2sO
4, the material dissolved through leaching enters next step;
(6) in solid-liquid separation device, material obtained in the previous step is carried out solid-liquid separation, the liquid phase material obtained enters the further separation and purification of the tenth step, and solid-phase material enters the further separation and purification of the 13 step;
(7) removal of impurities decolouring: in removal of impurities decolorizing and refining equipment, add adsorption-edulcoration agent molecule sieve adsorbant, consumption is 1.0% of solution quality, and the liquid phase material that the 4th step obtains is carried out removal of impurities decolorization operations, and what decolour through adsorption-edulcoration contains Pb
2+solution enters next step;
(8) solid-liquid separation: in any one solid-liquid separation equipment in solid-liquid separation device, material obtained in the previous step is carried out solid-liquid separation, the liquid phase material obtained enters the further separation and purification of the 9th step, and solid-phase material enters previous step after treatment and realizes recycling as adsorption-edulcoration agent;
(9) crystallisation by cooling: in cooling crystallizing equipment, by obtained in the previous step containing Pb
2+refined soln is cooled to 0 DEG C, Pb
2+salt-pepper noise is separated out, and obtains Pb through solid-liquid separation
2+product salt, the separation mother liquor obtained enters the liquid use of the 3rd step as the leaching of configuration acid solution after further separation, impurity removal;
(10) removal of impurities decolouring: in removal of impurities decolorizing and refining equipment, add adsorption-edulcoration agent diatomite, consumption is 1.0% of solution quality, and the liquid phase material that the 6th step obtains is carried out removal of impurities decolorization operations, through the PbSO of adsorption-edulcoration
4solution enters next step;
(11) solid-liquid separation: in solid-liquid separation device, material obtained in the previous step is carried out solid-liquid separation, the liquid phase material obtained enters the further separation and purification of the 12 step, and solid-phase material enters previous step after treatment and realizes recycling as adsorption-edulcoration agent;
(12) evaporative crystallization: stir in evaporation crystallization equipment in autoclave, material obtained in the previous step is carried out heat, decompression operation, the absolute pressure of evaporation deamination decompression operation is 0.08Ma, evaporate the solvent removed in solution and enter gas phase, enter vapor phase solvent enter the 5th step as leaching liquid realize recycle, while evaporative crystallization, PbSO
4crystallization, through solid-liquid separation, the liquid phase material obtained enters the 5th step and realizes recycling as leaching liquid, and solid-phase material is PbSO
4product;
(13) washing impurity-removing: in washing impurity-removing equipment, adds washings water, and the mass ratio of water add-on and plumbic oxide is 1:4;
(14) solid-liquid separation: in solid-liquid separation device, material obtained in the previous step is carried out solid-liquid separation, the liquid phase material obtained enters the 13 step and realizes recycling as washings after further separation and purification, and solid-phase material enters next step;
(15) drying and roasting: solid-phase material obtained in the previous step is carried out drying, roasting removing impurity, the solid-phase material obtained is PbO
2product.
The invention is not restricted to above-described embodiment, the technical scheme that all employings are equal to replacement or equivalence replacement formation all belongs to the scope of protection of present invention.Except the various embodiments described above, embodiment of the present invention also have a lot, and the technical scheme that all employings are equal to or equivalence is replaced, all within protection scope of the present invention.
Claims (10)
1. a PbO, PbSO
4, PbO
2the separation method of mixture, is characterized in that, be with the lead-containing material of waste lead accumulator through physical separation method process obtain containing PbO, PbSO
4, PbO
2the lead plaster of mixture is raw material, adopts acidleach to dissolve, leaches dissolving, separation and purification, solid-liquid separation coupling process, realize PbO, PbSO
4, PbO
2the separation of mixture; Step is as follows:
(1) washing impurity-removing: in washing impurity-removing equipment, by PbO, PbSO
4, PbO
2mixture carries out washing impurity-removing, removes soluble impurity, and the material through washing impurity-removing enters next step;
(2) solid-liquid separation: in solid-liquid separation equipment, material obtained in the previous step is carried out solid-liquid separation, the liquid phase material obtained enters (1) step and recycles as washings after further removal of impurities process, is separated the solid-phase material obtained and enters next step;
(3) acidleach is dissolved: in leaching dissolution equipment, add Acid leaching agent, with PbO, PbSO
4, PbO
2mixture mixes, and PbO wherein and acid react, and makes the PbO in material generate water-soluble Pb
2+ion enters solution, and the material dissolved through acidleach enters next step;
(4) solid-liquid separation: in solid-liquid separation equipment, material obtained in the previous step is carried out solid-liquid separation, the liquid phase material obtained obtains water-soluble lead salt or processes further obtaining PbO through further separation and purification, and the solid-phase material obtained enters next step;
(5) leaching is dissolved: in leaching dissolution equipment, add leaching agent and solid-phase material obtained in the previous step, the material dissolved through leaching enters next step;
(6) in solid-liquid separation equipment, material obtained in the previous step is carried out solid-liquid separation, the liquid phase material obtained enters the further separation and purification of (10) step, and solid-phase material enters the further separation and purification of (13) step;
(7) removal of impurities decolouring: in removal of impurities decolorizing and refining equipment, add adsorption-edulcoration agent, the liquid phase material that (4) step obtains is carried out removal of impurities decolouring, what decolour through adsorption-edulcoration contains Pb
2+solution enters next step;
(8) solid-liquid separation: in solid-liquid separation equipment, material obtained in the previous step is carried out solid-liquid separation, the liquid phase material obtained enters the further separation and purification of (9) step, solid-phase material reclaim after treatment adsorption-edulcoration agent enter previous step realize recycle;
(9) crystallisation by cooling: in cooling crystallizing equipment, cools liquid phase material obtained in the previous step, Pb
2+salt-pepper noise is separated out, and obtains Pb through solid-liquid separation
2+product salt, the separation mother liquor obtained enters (3) step and uses as preparating acid leaching agent after further separation, impurity removal;
(10) removal of impurities decolouring: in removal of impurities decolorizing and refining equipment, add adsorption-edulcoration agent, the liquid phase material that (6) step obtains is carried out removal of impurities decolouring, through the PbSO of adsorption-edulcoration
4solution enters next step;
(11) solid-liquid separation: in solid-liquid separation equipment, material obtained in the previous step is carried out solid-liquid separation, the liquid phase material obtained enters the further separation and purification of (12) step and enters next step, solid-phase material reclaim after treatment adsorption-edulcoration agent enter previous step realize recycle;
(12) evaporative crystallization: in evaporation crystallization equipment, is undertaken material obtained in the previous step heating, decompression operation, in solution evaporation remove solvent enter gas phase, this vapor phase solvent enters (5) step and realizes recycling as leaching liquid; While evaporative crystallization, PbSO
4crystallization, through solid-liquid separation, the liquid phase material obtained enters (5) step and realizes recycling as leaching liquid, and solid-phase material is PbSO
4product;
(13) washing impurity-removing: in washing impurity-removing equipment, add washings, carries out washing impurity-removing separation by the solid-phase material that (6) step obtains;
(14) solid-liquid separation: in solid-liquid separation equipment, material obtained in the previous step is carried out solid-liquid separation, the liquid phase material obtained enters (13) step and realizes recycling as washings after further separation and purification, and solid-phase material enters next step;
(15) drying and roasting: solid-phase material obtained in the previous step is carried out drying, roasting removing impurity, the solid-phase material obtained is PbO
2product.
2. PbO, PbSO according to claim 1
4, PbO
2the separation method of mixture, is characterized in that: the acid described in (3) step acidleach dissolution process is any one in nitric acid, acetic acid, citric acid, hexafluorosilicic acid, trifluoromethane sulfonic acid.
3. PbO, PbSO according to claim 1
4, PbO
2the separation method of mixture, is characterized in that: the leaching agent of (5) step leaching described in dissolution process is NH
3h
2o-(NH
4)
2sO
4or C
6h
8o
7h
2o-Na
3c
6h
5o
72H
2o or (NH
4)
2siF
6-H
2siF
6any one.
4. PbO, PbSO according to claim 1
4, PbO
2the separation method of mixture, it is characterized in that: (7) step removal of impurities decolouring and the removal of impurities sorbent material described in (10) step removal of impurities decolorization are the one in activated carbon, diatomite and adsorbent of molecular sieve, or the mixture of any two components or three components in them, the consumption of removal of impurities sorbent material is the 1.0%-5.0% of solution quality.
5. PbO, PbSO according to claim 1
4, PbO
2the separation method of mixture, is characterized in that: (9) step crystallisation by cooling temperature is 0 DEG C-20 DEG C.
6. PbO, PbSO according to claim 1
4, PbO
2the separation method of mixture, is characterized in that: the absolute pressure of (12) step evaporation deamination decompression operation is 0.01MPa-0.08MPa.
7. separation method according to claim 1, is characterized in that: PbO, PbSO during (2) step washing is separated
4, PbO
2the mass ratio of mixture and water is 1:1-1:10.
8. PbO, PbSO according to claim 1
4, PbO
2the separation method of mixture, it is characterized in that: the washings described in (13) step washing impurity-removing process is water, methyl alcohol, ethanol, or the mixture of any two components or three components in them, total add-on of described washing impurity-removing liquid and the mass ratio of plumbic oxide are 1:1-1:10.
9. PbO, PbSO according to claim 1
4, PbO
2the separation method of mixture, is characterized in that: in (15) step drying and roasting process, and drying temperature is 20 DEG C-200 DEG C, and maturing temperature is 200 DEG C-600 DEG C.
10. separation method according to claim 1, it is characterized in that: the washing impurity-removing liquid used in (1) step washing impurity-removing process is water, methyl alcohol, ethanol, or the mixture of any component in them, total add-on of described washing impurity-removing liquid is the mass ratio of solid-phase material and washing impurity-removing liquid is 1:1-1:10.
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|---|---|---|---|---|
| CN105200241A (en) * | 2015-11-02 | 2015-12-30 | 扬州大学 | Method for preparing PbO, PbSO4 and PbO2 from lead plaster of waste lead storage battery through separation |
| CN105923649A (en) * | 2016-04-14 | 2016-09-07 | 扬州大学 | Method for removing barium sulfate impurity from lead dioxide |
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| CN110512078A (en) * | 2019-07-30 | 2019-11-29 | 安徽华铂再生资源科技有限公司 | A kind of lead plaster melting processing technology |
| CN113363426A (en) * | 2021-06-04 | 2021-09-07 | 河北大学 | Preparation method of sodium ion battery based on metal Pb negative electrode and metal Pb recovery method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105200241A (en) * | 2015-11-02 | 2015-12-30 | 扬州大学 | Method for preparing PbO, PbSO4 and PbO2 from lead plaster of waste lead storage battery through separation |
| CN105923649A (en) * | 2016-04-14 | 2016-09-07 | 扬州大学 | Method for removing barium sulfate impurity from lead dioxide |
| CN109399698A (en) * | 2018-09-30 | 2019-03-01 | 超威电源有限公司 | A method of utilizing leaching clay standby four basic lead sulphates of lead plumbate |
| CN110512078A (en) * | 2019-07-30 | 2019-11-29 | 安徽华铂再生资源科技有限公司 | A kind of lead plaster melting processing technology |
| CN113363426A (en) * | 2021-06-04 | 2021-09-07 | 河北大学 | Preparation method of sodium ion battery based on metal Pb negative electrode and metal Pb recovery method |
| CN114317947A (en) * | 2021-12-14 | 2022-04-12 | 北京工业大学 | Method and device for two-stage mechanical reinforced desulfurization of waste lead paste |
| CN114317947B (en) * | 2021-12-14 | 2023-12-29 | 北京工业大学 | Method and device for mechanically strengthening desulfurization of waste lead plaster in two sections |
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