CN102689921A - Preparation method of Pb oxide nano powder for recovery and manufacture of lead acid battery - Google Patents
Preparation method of Pb oxide nano powder for recovery and manufacture of lead acid battery Download PDFInfo
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- CN102689921A CN102689921A CN2011100717256A CN201110071725A CN102689921A CN 102689921 A CN102689921 A CN 102689921A CN 2011100717256 A CN2011100717256 A CN 2011100717256A CN 201110071725 A CN201110071725 A CN 201110071725A CN 102689921 A CN102689921 A CN 102689921A
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- 239000008117 stearic acid Substances 0.000 claims description 2
- 238000005979 thermal decomposition reaction Methods 0.000 claims description 2
- OUYCCCASQSFEME-UHFFFAOYSA-N tyrosine Natural products OC(=O)C(N)CC1=CC=C(O)C=C1 OUYCCCASQSFEME-UHFFFAOYSA-N 0.000 claims description 2
- 239000004474 valine Substances 0.000 claims description 2
- 239000002888 zwitterionic surfactant Substances 0.000 claims description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 claims 2
- WBEHKXQILJKFIN-UHFFFAOYSA-N 2-amino-2-methyltetradecanoic acid Chemical compound CCCCCCCCCCCCC(C)(N)C(O)=O WBEHKXQILJKFIN-UHFFFAOYSA-N 0.000 claims 1
- DUIOKRXOKLLURE-UHFFFAOYSA-N 2-octylphenol Chemical compound CCCCCCCCC1=CC=CC=C1O DUIOKRXOKLLURE-UHFFFAOYSA-N 0.000 claims 1
- 238000005194 fractionation Methods 0.000 claims 1
- UTTVXKGNTWZECK-UHFFFAOYSA-N n,n-dimethyloctadecan-1-amine oxide Chemical compound CCCCCCCCCCCCCCCCCC[N+](C)(C)[O-] UTTVXKGNTWZECK-UHFFFAOYSA-N 0.000 claims 1
- 239000000843 powder Substances 0.000 abstract description 27
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 29
- 239000002245 particle Substances 0.000 description 24
- 239000002244 precipitate Substances 0.000 description 24
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 15
- 238000002441 X-ray diffraction Methods 0.000 description 13
- HTUMBQDCCIXGCV-UHFFFAOYSA-N lead oxide Chemical compound [O-2].[Pb+2] HTUMBQDCCIXGCV-UHFFFAOYSA-N 0.000 description 10
- 239000011259 mixed solution Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 238000004070 electrodeposition Methods 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000011160 research Methods 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- YADSGOSSYOOKMP-UHFFFAOYSA-N lead dioxide Inorganic materials O=[Pb]=O YADSGOSSYOOKMP-UHFFFAOYSA-N 0.000 description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 239000013543 active substance Substances 0.000 description 4
- 229910052924 anglesite Inorganic materials 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 4
- 238000002386 leaching Methods 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- KEQXNNJHMWSZHK-UHFFFAOYSA-L 1,3,2,4$l^{2}-dioxathiaplumbetane 2,2-dioxide Chemical compound [Pb+2].[O-]S([O-])(=O)=O KEQXNNJHMWSZHK-UHFFFAOYSA-L 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000004251 Ammonium lactate Substances 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 239000013504 Triton X-100 Substances 0.000 description 2
- 229920004890 Triton X-100 Polymers 0.000 description 2
- 229940059265 ammonium lactate Drugs 0.000 description 2
- 235000019286 ammonium lactate Nutrition 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- RZOBLYBZQXQGFY-HSHFZTNMSA-N azanium;(2r)-2-hydroxypropanoate Chemical compound [NH4+].C[C@@H](O)C([O-])=O RZOBLYBZQXQGFY-HSHFZTNMSA-N 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000009854 hydrometallurgy Methods 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- JQJCSZOEVBFDKO-UHFFFAOYSA-N lead zinc Chemical compound [Zn].[Pb] JQJCSZOEVBFDKO-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 239000002159 nanocrystal Substances 0.000 description 2
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 description 2
- 229920000053 polysorbate 80 Polymers 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 230000001698 pyrogenic effect Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- 239000010926 waste battery Substances 0.000 description 2
- STGNLGBPLOVYMA-TZKOHIRVSA-N (z)-but-2-enedioic acid Chemical compound OC(=O)\C=C/C(O)=O.OC(=O)\C=C/C(O)=O STGNLGBPLOVYMA-TZKOHIRVSA-N 0.000 description 1
- WJYAJBDKANFOID-UHFFFAOYSA-N 2-(dodecylamino)propanoic acid Chemical compound CCCCCCCCCCCCNC(C)C(O)=O WJYAJBDKANFOID-UHFFFAOYSA-N 0.000 description 1
- OORRCVPWRPVJEK-UHFFFAOYSA-N 2-oxidanylethanoic acid Chemical compound OCC(O)=O.OCC(O)=O OORRCVPWRPVJEK-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 229910004039 HBF4 Inorganic materials 0.000 description 1
- 239000007832 Na2SO4 Substances 0.000 description 1
- 229910004014 SiF4 Inorganic materials 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- XJMWHXZUIGHOBA-UHFFFAOYSA-N azane;propanoic acid Chemical compound N.CCC(O)=O XJMWHXZUIGHOBA-UHFFFAOYSA-N 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- ITHZDDVSAWDQPZ-UHFFFAOYSA-L barium acetate Chemical compound [Ba+2].CC([O-])=O.CC([O-])=O ITHZDDVSAWDQPZ-UHFFFAOYSA-L 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- FRRMMWJCHSFNSG-UHFFFAOYSA-N diazanium;propanedioate Chemical compound [NH4+].[NH4+].[O-]C(=O)CC([O-])=O FRRMMWJCHSFNSG-UHFFFAOYSA-N 0.000 description 1
- NAPSCFZYZVSQHF-UHFFFAOYSA-N dimantine Chemical compound CCCCCCCCCCCCCCCCCCN(C)C NAPSCFZYZVSQHF-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000005242 forging Methods 0.000 description 1
- 238000004508 fractional distillation Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910000464 lead oxide Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- NIFHFRBCEUSGEE-UHFFFAOYSA-N oxalic acid Chemical compound OC(=O)C(O)=O.OC(=O)C(O)=O NIFHFRBCEUSGEE-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229920000136 polysorbate Polymers 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000009853 pyrometallurgy Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000007704 wet chemistry method Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
Landscapes
- Processing Of Solid Wastes (AREA)
- Secondary Cells (AREA)
Abstract
The invention discloses a preparation method of a Pb oxide nano powder for recovery and manufacture of a lead acid battery. The method comprises the steps of: (1) reacting lead salt or waste lead acid battery lead paste with an organic or inorganic compound capable of complexing with Pb atom / ion, so as to realize desulphurization or reloading of acid radical; and (2) carrying out treatment processes of filtering, drying for removing water and heating for decomposition, so as to obtain the Pb oxide nano powder. The method of the invention realizes an environment-friendly and energy-efficient recovery and production process with substantially reduced production cost; meanwhile, the prepared Pb oxide powder is beneficial for enhancement of product performance.
Description
Technical Field
The invention relates to preparation of Pb (lead) oxide nano powder, in particular to a preparation method of Pb oxide nano powder for recovery and manufacture of a lead-acid storage battery.
Background
Compared with other commercialized storage batteries, the lead-acid storage battery has good recycling characteristics. This is because lead, which is a main raw material constituting the battery, is better recycled. Early methods for recovering lead mainly include the earth-fire method, i.e., melting the lead paste of waste batteries using a reverberatory furnace, a blast furnace, or the like. PbSO in general lead paste4The content of the lead-acid battery lead paste is more than 50 percent, the melting point is high, the complete decomposition temperature is more than 1000 ℃ (Yanjia wide, the research progress of the lead paste recovery technology of the waste lead-acid battery is [ J]Modern chemical industry, 2009, 29 (3). In order to overcome the high energy consumption and high energy consumption of the pyrometallurgyPollutant emission (emission of large amount of SO)2And metal volatile gas), many scholars at home and abroad research on the desulfurization pyrogenic process [ maqiang, zuo dongmei, et al, shallow-educing wet treatment process of waste storage batteries [ J]The university journal of high-tech, electromechanical, in south of the river, 2008, 16 (3): 77-78; chenmengjie, wet treatment of waste lead battery plate powder to recover lead, proceedings of the sixth academic annual meeting of the Chinese granular society and the particle technology seminars on both sides of the strait, 2008; lyakov N K, Atananova D A, et al, Desulphurization of sampled Battery by sodium carbonate and sodium hydroxide [ J]Journal of Power Sources, 2007, 171 (2): 960-2CO3And desulfurizer such as NaOH is used for removing PbSO in the lead plaster4Conversion to soluble NaSO4And insoluble Pb2CO3Or Pb (OH)2And (4) precipitating. Due to PbCO3Low decomposition temperature of compounds, desulfurized PbCO3The compounds can be decomposed at a lower temperature (at least 100 to 150 ℃ lower than that of the non-desulfurized compound), Na2SO4Can be sold as a by-product. Due to the problem of desulfurization conversion, about 5% of PbSO is also generated4SO remains in the lead paste after conversion, SO is also found in general smelting after conversion2And (4) generating. In order to solve the environmental problem caused by the pyrogenic process, an electrodeposition method (abbreviated as electrodeposition method) is introduced. The main process is conversion-leaching (with H)2SiF4Or HBF4Solution) -electrodeposition. Other similar methods are direct leaching-electrodeposition without transformation, and direct lead paste electrodeposition [ Yanjiakui, development of lead paste recovery technology for waste lead acid batteries [ J]Modernization, 2009, 29 (3); new technological development of secondary lead from Luke source [ J]Resource regeneration, 2007 (11). The electrodeposition method solves the problem of SO in pyrometallurgy2The emission and the volatilization of lead at high temperature, but the process has large investment, is only suitable for building a large-scale recovery plant, and still does not solve the problem of high energy consumption.
Lead plaster of waste lead-acid storage batteries is recovered by a wet method and directly converted into active substance PbO superfine powder of the batteriesThe new and better recovery processing idea is that, on one hand, the environmental protection problem is solved, the technical processes of smelting or electrodeposition, forging and pressing, ball milling and the like are simplified, and on the other hand, the method can also play an important role in improving the performance of the lead-acid storage battery. The international lead-zinc research organization (ILZRO) sets up a significant project to develop the research on the active substances of lead-acid batteries, wherein Schrade Phd [ Yanjiakui ] researches on the lead paste recycling technology of waste lead-acid batteries [ J]Modernization, 2009, 29 (3); F.R S. development insert-acid Battery technology [ C ]](JE.Dutriac.Lead-Zinc 2000,Proc ofthe lead-Lead-Zinc 2000 Symp TMS Fall Extraction &process metallurygMeeting.2000. Pittabourg: TMS): 887-897 researches show that the lead-acid storage battery prepared from the ultrafine PbO particles has the characteristics of high capacity and long charge-discharge life, and has the defect of high cost for preparing the ultrafine PbO particles. Recently, Karami [ Sonmez M S and Kumar R V.Leaching of waste bat typate compositions.part 2: leaching and depletion of PbSO4 bylcitic acid and sodium citrate solution [ J].Hydrometallurgy,2009,95(1-2):82-86;Sonmez M S and Kumar R V.Leaching of waste battery pastecomponents.Part 1:Lead citrate synthesis from PbO and PbO2 [J]Hydrometallurgy, 2009, 95 (1-2): 53-60, etc., adopting ultrasonic auxiliary technique, using polyvinylpyrrolidone (PVP) as guide agent and using Pb (NO) as guide agent3)2The nano-crystalline PbO is synthesized and applied to the active material of the lead-acid storage battery electrode, and shows excellent capacity and service life. The invention patent with Chinese patent number 02100264.9 (publication number CN 1171797C) also discloses a method for synthesizing alpha and beta type lead dioxide nanocrystals and lead trioxide nanocrystals, but the prepared Pb oxide does not conform to the requirements of the existing mature lead-acid storage battery manufacturing process.
In addition, the invention patent application with the Chinese patent application number of 200780041628.4 (publication number CN101573461A) discloses lead recovery and Chinese new peaks (Zhuxinfeng, Liuwan super, etc., lead paste of waste lead-acid batteries is used for preparing superfine lead oxide powder [ J ], Chinese non-ferrous metal science report, 2010(1), etc., the recovery of lead is researched by adopting a citric acid method, the recovery of the lead paste of waste lead-acid batteries is directly converted into active substance material PbO superfine powder of batteries, and the particle size of the powder is 200-500 nm.
In the method for preparing the Pb oxide powder, the process cost is too high, or the method is not suitable for the existing recovery and manufacturing process of the lead-acid storage battery, and is difficult to be applied to commercial production.
Disclosure of Invention
The invention aims to solve the technical problem of providing a method for preparing Pb oxide nano powder for recycling and manufacturing a lead-acid storage battery. The method is simple, environment-friendly and low in consumption, and the performance of the prepared lead-acid storage battery can be obviously improved by utilizing the Pb oxide nano powder.
In order to solve the technical problems, the method for preparing the Pb oxide nano powder for the recovery and the manufacture of the lead-acid storage battery comprises the following steps:
(1) lead paste (mainly containing Pb and PbO) of lead salt or waste lead-acid storage battery2、PbO、PbSO4) Reacting (interacting) with an organic or inorganic compound (in liquid phase) capable of complexing Pb atoms/ions, SO as to obtain Pb atoms/ions and Sulphate (SO)4) The ions or other acid radicals are separated from each other, namely, the desulfurization or the reacidification is realized;
among them, lead salts include various inorganic acid lead salts and various organic acid lead salts, such as including: lead sulfate, lead nitrate, lead chloride, lead phosphate, lead chromate, lead molybdate, lead ferrite, lead carbonate, lead oxalate, lead stearate, lead acetate, lead citrate, and the like;
the temperature range of the reaction in the step (1) is below 1000 ℃;
(2) and (3) filtering, drying to remove water and heating to decompose (the heating temperature is below 800 ℃) the generated new lead salt compound or mixture or solution to obtain the Pb oxide nano powder.
In the step (1), the characteristics of the organic or inorganic compound capable of complexing Pb atoms/ions mainly include: the compound contains O (oxygen) or/and nitrogen or/and sulfur or/and phosphorus lone pair electrons or carbonyl or/and carboxyl or/and amine groups in the molecular structure and compounds containing large pi bonds, and can be organic acid or/and salts thereof, inorganic acid or/and salts thereof and other organic compounds containing the functional groups. For example, the organic or inorganic compounds include: carbonic acid, formic acid, acetic acid, propionic acid, oxalic acid (oxalic acid), malonic acid, lactic acid, citric acid, maleic acid (maleic acid), ethylenediaminetetraacetic acid (EDTA), polyacrylic acid (PAA, molecular weight 10-10000000), polyacrylate (molecular weight 10-10000000), polymaleic acid (PMA, molecular weight 10-10000000), formic acid, tartaric acid, fumaric acid, phthalic acid, maleic acid, oxalic acid, malic acid, salts of these compounds, mixtures of these compounds and salts thereof, and urea. Wherein the molar concentration ratio of the organic or inorganic compound is as follows: the ratio of Pb atoms/ions to the compound is 1: 0.1-1: 1000.
In the step (1), a surfactant can be further added into the reaction system to help Pb and SO4The separation of the ions facilitates the subsequent dispersion or modification of the nanoparticles. The surfactant comprises: anionic surfactants (such as stearic acid or/and oleic acid or/and lauric acid and salts thereof), cationic surfactants (such as cetylpolyoxyethylene ether-based dimethyloctane ammonium chloride or/and dodecyldimethylbenzylammonium chloride), zwitterionic surfactants (such as cocamidopropyl betaine or/and dodecylaminopropionic acid or/and octadecyldimethylammonium oxide), nonionic surfactants [ such as the isomeric alcohol polyoxyethylene polyoxypropylene ethers or/and polyvinylpyrrolidone (PVP) or/and octylphenol polyoxyethylene ether (Triton X-100) or/and polyethylene glycol octylphenyl ether (emulsifier OP) or/and polyoxyethylene sorbitan fatty acid esters (Tween) ]. Wherein, the molar concentration ratio of the added surfactant is as follows: the ratio of Pb atoms/ions to surfactant is 1: 0.0001-1: 10.
In the step (1), a reducing agent or/and an oxidizing agent can be added, and the method comprises the following steps: CO, H2O2、FeSO4、O2And air. Wherein, the molar concentration ratio of the reducing agent or/and the oxidizing agent is as follows: the ratio of Pb atoms/ions to the reducing agent or/and the oxidizing agent is 1: 0.01-1: 100.
In the step (1), a complexing agent for impurity metal ions may be further added to the reaction system to form a soluble complex. Wherein, impurity metal ions include: ca. Cd, Sn, Ag, Cu, Fe, Bi, As, Sb, Zn, Ni, Ba and other ions; a complexing agent for impurity metal ions comprising: ethylenediaminetetraacetic acid (EDTA), 1, 2-diaminopropane-N' -tetraacetic acid (DPTA), amino acids, glycolic acid (glycolic acid), organic acids, bases, and salts thereof. Wherein,
the molar concentration ratio of the added complexing agent of the impurity metal ions is as follows: the complexing agent of Pb atoms/ions and impurity metal ions is between 1: 0.0001 and 1: 10.
Wherein the amino acids include: glycine, alanine, tryptophan, glutamic acid, valine, leucine, isoleucine, proline, phenylalanine, methionine, serine, threonine, cysteine, tyrosine, asparagine, glutamine, lysine, arginine, histidine, aspartic acid;
the organic acids include: formic acid, acetic acid, propionic acid, oxalic acid, malonic acid, lactic acid, citric acid, maleic acid, ethylenediamine tetraacetic acid, polyacrylic acid, polyallylene, polymaleic acid, formic acid, tartaric acid, fumaric acid, phthalic acid, maleic acid, oxalic acid, malic acid;
the base comprises: ammonia (ammonium), ethylene diamine (ethylenediamine), tetramethylammonium hydroxide (TMAH).
In the step (2), the decomposition gas generated from the reactant in the heating process and/or the gas (such as CO or CO) generated from the combustion process may be used2Etc.) is introduced into the step (1) to be used as a reducing agent or a complexing agent.
In the step (2), before the thermal decomposition treatment, the new lead salt compound and the solution may be subjected to other treatments such as fractional distillation or/and extraction to separate the lead-containing compound from other non-lead-containing compounds or solvents.
In addition, in the steps (1) and (2), other physical action modes can be assisted, including: ultrasound, overweight, microwave irradiation, UV irradiation, etc. to facilitate the reaction or action.
In the step (2), the obtained Pb oxide nano powder has a particle size of less than 100nm, and the Pb oxide with a particle size of 100 nm-3000 nm can also be obtained.
Compared with other related methods in the recovery or manufacturing process of lead-acid storage batteries or the preparation method of Pb oxide nano powder, the method disclosed by the invention mainly reflects the differences of the compounds or the compositions of the compounds in the disclosed process, the process steps or the process routes and the obtained results and effects, and has the following specific beneficial effects:
(1) the wet chemical process is mainly used, so that the recovery and production process is environment-friendly and has low energy consumption;
(2) the process complexity is reduced, and some logistic steps in the existing recovery and production processes are reduced, so that the production cost can be greatly reduced, and the production period is shortened;
(3) the size of the obtained Pb oxide powder particles can reach the size of a nano material (generally 0.1-100 nm), and the size, the shape, the structure, the dispersity and the compoundability with other materials of the Pb oxide particles can be adjusted through the selection of reaction conditions in each step, so that the prepared Pb oxide powder is more favorable for improving the performance of a process product, namely, the Pb oxide nano powder for producing a new lead-acid storage battery is processed by using an ineffective active substance or a metal lead block of a waste lead-acid storage battery, the existing process and related logistic steps are simplified, and the performance of the prepared lead-acid storage battery is also obviously improved.
Drawings
The invention will be described in further detail with reference to the following detailed description and accompanying drawings:
the attached figure is a schematic flow chart of the preparation method of the invention.
Detailed Description
Lead paste of waste lead-acid battery is known as a mixture containing Pb, PbO as main substances2、PbSO4Having molar masses of 207g/mol, 223g/mol, 239g/mol, 303g/mol, respectively, wherein, relatively, PbSO4、PbO2The content is large. Minor amounts of other ingredients are also present. The relative content ratio of the substances in the lead plaster of the waste lead-acid battery can vary with the type, the use state and other factors of the primary lead-acid battery. Therefore, in the following examples, the weight of the lead paste is calculated as the molar content of lead in the lead paste by taking the average molar mass (200 to 300g/mol) of the mixture. The specific mixed mean molar masses employed in the individual examples are stated in the respective examples, if not stated, to be 271g/mol, (i.e.molar proportions of 50% PbSO)4+50%PbO2) The estimation is performed.
Example 1
The invention discloses a method for preparing Pb oxide nano powder for lead-acid battery recovery and manufacture, which has a flow schematic diagram, as shown in the attached drawing of the specification, and comprises the following steps:
(1) 0.1kg (0.308mol) of lead acetate was placed in 0.9kg of water, and then 0.136kg (3.08mol) of CO was passed through the water2To form carbonic acid solution, and simultaneously react with lead acetate to generate precipitate, and the reaction is carried out at room temperatureThe reaction time is controlled until no precipitation continues to occur, and a precipitate A is generated;
separately, 1kg of the above lead acetate solution was prepared in the same manner, 0.02kg (0.0308mol) of Triton X-100 as a surfactant was added thereto, and then CO was introduced in the same manner2In the process, 30s of ultrasound is assisted to the reaction system at an interval of 2 minutes to generate a precipitate B;
(2) filtering the solution to respectively obtain precipitates A and B, drying at the temperature of less than or equal to 200 ℃ to remove water, then heating and decomposing at the temperature of 300-500 ℃ for 1-30 min to respectively obtain powders A and B, and observing by a Transmission Electron Microscope (TEM), and analyzing by X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS), wherein the obtained Pb oxide nano powder has the particle size of 1-90 nm and the particle size of 0.1-70 nm.
Example 2
The invention relates to a method for preparing Pb oxide nano powder for recycling and manufacturing lead-acid storage batteries, which comprises the following steps:
(1) 0.1kg of lead sulfate (0.33mol) was mixed with 1 liter of Na having a concentration of 1.65mol/L2CO3The aqueous solution is reacted, the solution is removed after the reaction, and then the precipitate is mixed with 1 liter of Na with the concentration of 1.65mol/L2CO3The aqueous solution was reacted 200 times in such a way that 0.1kg of lead sulfate (0.33mol) was reacted with 333mol of Na in total2CO3Interacting, and fully removing sulfur to obtain a precipitate A;
further, the above Na was prepared in the same manner as above2CO3The solution was added with 0.007kg (0.0165mol) of Tween-80 as a surfactant, and the same operation was repeated, and the reaction system was subjected to ultrasonic treatment for 30 seconds during the interaction (reaction), so as to remove Na2CO3Besides the interaction, 0.1kg of lead sulfate (0.33mol) also interacted with a total of 3.3mol (1.412kg) of Tween-80, and finally a precipitate B was obtained;
(2) filtering the solution to respectively obtain precipitates A and B, drying at the temperature of less than or equal to 200 ℃ to remove water, then heating and decomposing at the temperature of 300-500 ℃ for 1-30 min to respectively obtain powders A and B, and observing by a Transmission Electron Microscope (TEM), and analyzing by X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS), wherein the obtained Pb oxide nano powder has the particle size of 1-90 nm and the particle size of 0.1-70 nm.
Example 3
The invention relates to a method for preparing Pb oxide nano powder for recycling and manufacturing lead-acid storage batteries, which comprises the following steps:
(1) 0.1kg (0.303mol) of lead nitrate was placed in 3kg of water, and then 13.33kg (303mol) of CO was continuously introduced into the water2So as to form carbonic acid solution, and simultaneously react with lead nitrate to generate precipitate, wherein the reaction is carried out at room temperature, and the reaction time is controlled until no precipitate continues to occur, so as to generate precipitate A;
further, the above-mentioned 0.1kg (0.302mol) lead nitrate solution was similarly prepared, and 3.02mol (0.6kg) of lauric acid as a surfactant (or added together with a certain amount, e.g., 1kg, of an ethanol solvent) was added thereto, and the reaction system was subjected to the same CO-introducing operation with the ultrasonic wave while stirring, followed by the same CO-introducing operation2To produce a precipitate B;
(2) filtering the solution or/and the oily liquid to respectively obtain precipitates A and B, drying at the temperature of less than or equal to 200 ℃ to remove water, then heating and decomposing at the temperature of 300-500 ℃ for 1-30 min to respectively obtain powders A and B, and observing by a Transmission Electron Microscope (TEM), and analyzing by X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS), wherein the obtained Pb oxide nano powder has the particle size of 1-90 nm and the particle size of 0.1-70 nm.
Example 4
The invention relates to a method for preparing Pb oxide nano powder for recycling and manufacturing lead-acid storage batteries, which comprises the following steps:
(1) 0.1kg (0.1mol) of lead citrate was placed in 1kg of water, and then 0.0005kg (0.01 mol) of lead citrate was continuously introduced into the water)CO2Forming a carbonic acid solution, and simultaneously reacting with lead citrate, wherein the reaction is carried out at room temperature, and the reaction time is controlled to be 30min, so as to obtain a precipitate A;
separately, a mixed solution of 0.1kg (0.1mol) of the above lead citrate and water was prepared in the same manner, 0.00001mol (0.001kg) of a surfactant PVP (average molecular weight: 100000) was added thereto, the reaction system was subjected to ultrasonic treatment while stirring, and then CO was introduced in the same manner2To obtain a precipitate B;
(2) filtering the solution to respectively obtain precipitates A and B, drying at the temperature of less than or equal to 200 ℃ to remove water, then heating and decomposing at the temperature of 300-500 ℃ for 1-30 min to respectively obtain powders A and B, and observing by a Transmission Electron Microscope (TEM), and analyzing by X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS), wherein the obtained Pb oxide nano powder has the particle size of 1-90 nm and the particle size of 0.1-70 nm.
Example 5
The invention relates to a method for preparing Pb oxide nano powder for recycling and manufacturing lead-acid storage batteries, which comprises the following steps:
(1) placing 0.1kg of waste lead-acid storage battery lead plaster (the molar content of Pb is 0.33mol, which is estimated by the mixed molar mass of 300g/mol) in 0.9kg of 20% (mass concentration) citric acid solution, adding 0.01kg of surfactant oleic acid (which can be added together with a certain amount of ethanol, such as 0.05 kg), and reacting at room temperature until the color of the mixture of reactants and products is not changed, so as to realize desulfurization and generate a product A;
in addition, on the basis of the same operation, 0.000374kg, 0.0374kg or 3.74kg of 30% (mass concentration) H was added to the system2O2And 0.0005Kg or 0.01Kg of FeSO4Finally, a product B is generated;
(2) and filtering the solution to obtain products A and B respectively, drying the products at the temperature of less than or equal to 200 ℃ to remove water, then heating and decomposing the products at the temperature of 300-500 ℃ for 1-30 min to obtain powder A and powder B respectively, and observing the powder A and the powder B by using a TEM (transmission electron microscope), and analyzing the powder by using an XRD (X-ray diffraction) and an XPS (X-ray diffraction) to obtain the Pb oxide nano-powder, wherein the particle size of the powder A is 0.1-60 nm, and the particle size of the powder B.
In this step, the reaction product A is again reacted under overweight conditions. The acceleration of gravity used is 2 g. The same operation is performed to obtain Pb oxide nanopowder of 0.2-150 nm.
Example 6
The invention relates to a method for preparing Pb oxide nano powder for recycling and manufacturing lead-acid storage batteries, which comprises the following steps:
(1) putting 0.1kg of waste lead-acid storage battery lead plaster into a mixed solution prepared from 0.2kg of acetic acid, 0.05kg of barium acetate and 0.65kg of water, introducing a reducing agent CO, reacting until the lead plaster is completely dissolved (except for a small amount of impurity precipitate), and performing the reaction at 15-90 ℃ to realize desulfurization;
(2) filtering the solution, crystallizing the solution at a temperature of less than or equal to 100 ℃, drying to remove water, heating and decomposing at 100-500 ℃ for 1-30 min to obtain powder, and analyzing by TEM observation, XRD and XPS to obtain Pb oxide nano powder with a particle size of 0.1-65 nm.
At the same time, the gas (mainly CO) generated in the combustion process is heated and decomposed2CO generated by reaction with carbon) is introduced into the step (1) and utilized as a reducing agent, and then the same operation as described above is performed, and the obtained Pb oxide nanopowder is the same as the above result.
And (3) adding microwave irradiation to the steps (1) and (2) to obtain the Pb oxide nano powder with the similar size.
Example 7
The invention relates to a method for preparing Pb oxide nano powder for recycling and manufacturing lead-acid storage batteries, which comprises the following steps:
(1) 0.1kg of waste lead-acid storage battery lead paste (estimated as a mixed molar mass of 300g/mol)0.33mol of Pb) was reacted with 0.9kg of a mixed solution containing 0.05kg of ammonium propionate, 0.1kg of ammonium oxalate, 0.05kg of ammonium malonate and 0.05kg of ammonium lactate, and 1.25X 10 times 1kg of ammonium lactate was also added to the mixed solution-5Or 0.01 or 0.187kg of complexing agent EDTA or 1.25kg of EDTA and 5kg of H2The mixture of O is reacted at room temperature and stirred for 0.1-2 hours, so that full desulfurization is realized;
(2) filtering the solution, drying and dewatering at 90 ℃ to obtain a solid product, then heating and decomposing at 200-600 ℃, and radiating UV radiation while heating. According to TEM observation, XRD and XPS analysis, the finally obtained powder is Pb oxide nano powder, and the particle size is 0.1-85 nm.
Example 8
The invention relates to a method for preparing Pb oxide nano powder for recycling and manufacturing lead-acid storage batteries, which comprises the following steps:
(1) 0.1kg of waste lead-acid battery lead paste was reacted with 0.9kg of the mixed solution. The mixed solution contains 0.01kg of citric acid, 0.02kg of maleic acid, 0.2kg of polyacrylic acid (molecular weight: 4000), 0.05kg of urea, 0.001kg of surfactant cetyl alcohol polyoxyethylene ether dimethyl octane ammonium chloride, and 0.01kg of oxidant H2O2(30 percent, mass concentration), 0.02kg of complexing agent glycine and 0.01kg of formic acid, the reaction is carried out at the temperature of 20-90 ℃, and the stirring is carried out for 30min, so as to realize the desulfurization and impurity removal; wherein, UV irradiation can be assisted in the step, and finally the solution containing the precipitate is obtained;
(2) filtering the solution to obtain a precipitate, drying at 60-80 ℃ to remove water, and then heating and decomposing at 150-650 ℃ to obtain powder. According to TEM observation, XRD and XPS analysis, the finally obtained powder is Pb oxide nano powder, and the particle size is 0.1-95 nm.
Example 9
The invention relates to a method for preparing Pb oxide nano powder for recycling and manufacturing lead-acid storage batteries, which comprises the following steps:
(1) 0.1kg of waste lead-acid battery lead paste was put into 0.9kg of the mixed solution to be reacted. The mixed solution contains 0.1kg of carbonic acid, 0.05kg of polyacrylate, 0.05kg of polymaleic acid and 0.10kg of sodium carbonate salt, and 0.02kg of surfactant isomerous alcohol polyoxyethylene polyoxypropylene ether, 0.03kg of complexing agent ethylenediamine and the balance of water, and the mixed solution is reacted at room temperature to realize desulfurization and impurity removal and simultaneously pre-disperse the precipitation product; wherein, ultrasound can be used as an auxiliary in the step;
(2) filtering the solution to obtain a precipitate, drying the precipitate at 50-100 ℃ to remove water, heating and decomposing the precipitate at 200-750 ℃ for 1-60 min to obtain powder, and finally obtaining the Pb oxide nano powder with the particle size of 0.1-3000 nm by TEM observation, XRD and XPS analysis.
Example 10
The invention relates to a method for preparing Pb oxide nano powder for recycling and manufacturing lead-acid storage batteries, which comprises the following steps:
(1) 0.1kg of waste lead-acid battery lead plaster is placed in 0.9kg of 30% (mass concentration) ammonium carbonate solution, and CO is introduced into the solution2Carrying out reaction at 15-90 ℃ for 60min to realize desulfurization;
(2) filtering the solution, taking a solid precipitate, drying and dehydrating at the temperature of less than or equal to 200 ℃, then heating and decomposing at the temperature of 200-500 ℃ for 1-30 min to obtain powder, and obtaining Pb oxide nano powder with the particle size of 0.1-120 nm through TEM observation, XRD and XPS analysis.
At the same time, the gas (mainly CO) generated in the combustion process is heated and decomposed2) The CO is utilized and is introduced into the step (1) to become CO which reacts with the lead plaster of the next batch of waste lead-acid storage batteries2A source of supply.
Example 11
The invention relates to a method for preparing Pb oxide nano powder for recycling and manufacturing lead-acid storage batteries, which comprises the following steps:
(1) 0.1kg of waste lead-acid storage battery lead paste is placed in 0.9kg of 30% (mass concentration) carbonic acid solution, and CO is introduced into the solution2Carrying out reaction at 5-95 ℃ for 60min to realize desulfurization;
(2) filtering the solution, taking a solid precipitate, drying and dehydrating at the temperature of less than or equal to 200 ℃, then heating and decomposing at the temperature of 200-500 ℃ for 1-30 min to obtain powder, and obtaining Pb oxide nano powder with the particle size of 0.1-120 nm through TEM observation, XRD and XPS analysis.
Simultaneously, heating the filtrate at a temperature of more than or equal to 30 ℃ to decompose or fractionate H in the filtrate2CO3、H2SO4And CO2+H2And O. Obtained H2CO3、CO2+H2O is utilized and is introduced into the step (1) to become CO which reacts with the next batch of waste lead-acid storage battery lead plaster2A source of supply, H2SO4Is used as a raw material for lead paste.
Claims (10)
1. A method for preparing Pb oxide nano powder for recycling and manufacturing lead-acid storage batteries comprises the following steps:
(1) the lead salt or the waste lead-acid storage battery lead plaster reacts with an organic or inorganic compound capable of complexing Pb atoms/ions to realize desulfurization or acid reacidification;
(2) and carrying out the treatment processes of filtering, drying to remove water and heating for decomposition to obtain the Pb oxide nano powder.
2. The method of claim 1, wherein: in the step (1), the lead salt includes: lead sulfate, lead nitrate, lead chloride, lead phosphate, lead chromate, lead molybdate, lead ferrite, lead carbonate, lead oxalate, lead stearate, lead acetate and lead citrate;
the characteristics of organic or inorganic compounds capable of complexing Pb atoms/ions mainly include: the compound contains oxygen or/and nitrogen or/and sulfur or/and phosphorus lone pair electrons or carbonyl or/and carboxyl or/and amine group in the molecular structure and a compound with a large pi bond; wherein the molar concentration ratio of the compound added is as follows: the ratio of Pb atoms/ions to the compound is 1: 0.1-1: 1000;
the temperature range of the reaction in the step (1) is below 1000 ℃.
3. The method of claim 2, wherein: in the step (1), the organic or inorganic compound capable of complexing Pb atoms/ions comprises: carbonic acid, formic acid, acetic acid, propionic acid, oxalic acid, malonic acid, lactic acid, citric acid, maleic acid, ethylenediamine tetraacetic acid, polyacrylic acid, polyacrylate, polymaleic acid, formic acid, tartaric acid, fumaric acid, phthalic acid, maleic acid, oxalic acid, malic acid, and salts of these compounds, and mixtures of these compounds and salts thereof, and urea.
4. The method of claim 1, wherein: in the step (1), a surfactant can be further added into the reaction system, and the surfactant comprises: anionic surfactants, cationic surfactants, zwitterionic surfactants, nonionic surfactants; wherein, the molar concentration ratio of the added surfactant is as follows: the ratio of Pb atoms/ions to surfactant is 1: 0.0001-1: 10.
5. The method of claim 4, wherein: the surfactant includes: stearic acid or/and oleic acid or/and lauric acid and salts thereof, cetyl alcohol polyoxyethylene ether dimethyl octane ammonium chloride, dodecyl dimethyl benzyl ammonium chloride, cocamidopropyl betaine, dodecyl amino propionic acid, octadecyl dimethyl amine oxide, isomeric alcohol polyoxyethylene polyoxypropylene ether, polyvinylpyrrolidone, octyl phenol polyoxyethylene ether, polyethylene glycol octyl phenyl ether and polyoxyethylene sorbitan fatty acid ester.
6. The method of claim 1, wherein: in the step (1), a reducing agent or/and an oxidizing agent can be added, and the method comprises the following steps: CO, H2O2、FeSO4、O2Air; wherein, the molar concentration ratio of the reducing agent or/and the oxidizing agent is as follows: the ratio of Pb atoms/ions to the reducing agent or/and the oxidizing agent is 1: 0.01-1: 100.
7. The method of claim 1, wherein: in the step (1), a complexing agent for impurity metal ions can be added into the reaction system, and the complexing agent comprises: ethylenediaminetetraacetic acid, 1, 2-diaminopropane-N' -tetraacetic acid, amino acids, glycolic acid, organic acids, bases, and salts thereof; wherein, the molar concentration ratio of the added complexing agent of the impurity metal ions is as follows: the complexing agent of Pb atoms/ions and impurity metal ions is between 1: 0.0001 and 1: 10.
8. The method of claim 7, wherein: the amino acids include: glycine, alanine, tryptophan, glutamic acid, valine, leucine, isoleucine, proline, phenylalanine, methionine, serine, threonine, cysteine, tyrosine, asparagine, glutamine, lysine, arginine, histidine, aspartic acid;
the organic acids include: formic acid, acetic acid, propionic acid, oxalic acid, malonic acid, lactic acid, citric acid, maleic acid, ethylenediamine tetraacetic acid, polyacrylic acid, polyallylene, polymaleic acid, formic acid, tartaric acid, fumaric acid, phthalic acid, maleic acid, oxalic acid, malic acid;
the base comprises: ammonia, ethylenediamine, tetramethylammonium hydroxide.
9. The method of claim 1, wherein: in the step (2), the heating temperature range is below 800 ℃;
in the step (2), decomposition gas generated by reactants in the heating process and/or gas generated in the combustion process can be introduced into the step (1) to be used as a reducing agent or a complexing agent for utilization;
in the step (2), fractionation and/or extraction may be performed before the thermal decomposition treatment.
10. The method of claim 1, wherein: in the steps (1) and (2), a physical action mode can be assisted, and the method comprises the following steps: ultrasound, overweight, microwave irradiation, UV irradiation.
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