CN102689921B

CN102689921B - The preparation method for the Pb nm-class oxide powders for reclaiming and manufacturing for lead-acid accumulator

Info

Publication number: CN102689921B
Application number: CN201110071725.6A
Authority: CN
Inventors: 杨春晓; 徐志国
Original assignee: Individual
Current assignee: Individual
Priority date: 2011-03-24
Filing date: 2011-03-24
Publication date: 2017-08-08
Anticipated expiration: 2031-03-24
Also published as: CN102689921A

Abstract

The invention discloses a kind of preparation method for the Pb nm-class oxide powders for reclaiming and manufacturing for lead-acid accumulator, including step：(1) lead salt or waste lead acid battery lead cream are reacted with that can be complexed the organic or inorganic compound of Pb atoms/ion, realize desulfurization or again acid group；(2) filtered, dry water removal, the processing procedure of heat resolve, obtain Pb nm-class oxide powders.The present invention makes recovery and production process environmental protection, low power consuming, substantially reduces production cost, while shortening the production cycle, and prepared Pb oxide powders is more beneficial for the raising of handicraft product performance.

Description

Method for preparing Pb oxide nano powder for recovery and manufacture of lead-acid storage battery

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 pollution emission (large amount of SO emission) of the pyrometallurgical method₂And metal volatile gas), many scholars at home and abroad carry out the research of the pre-desulfurization pyrogenic processWet processing technology for shallow educing waste accumulator [ J ] of Zhao Dong Mei, Zhao]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 bat type 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.

The wet recovery of the lead plaster of the waste lead-acid storage battery and the direct conversion of the lead plaster into the active material PbO superfine powder of the battery are a new and better recovery processing idea, because, on one hand, the environmental protection problem is solved, the process procedures of smelting or electrodeposition, forging and pressing, ball milling and the like are simplified,on the other hand, it may 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); RS.developments in lead-acid Battery technology [ C ]](JE.Dutriac.Lead-Zinc 2000，Proc of the 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 [ SonmezM S and Kumar R V.Leaching of waste Battery compositions.part 2: leachingand desulfurring of PbSO4 by citric acid and sodium citrate solution [ J].Hydrometallurgy，2009，95(1-2)：82-86；Sonmez M S and Kumar R V.Leaching ofwaste battery paste components.Part 1：Lead citrate synthesis from PbO andPbO2 [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 invention patent with Chinese patent No. 02100264.9 (publication No. CN 1171797C) also discloses a method for synthesizing α and β type lead dioxide nanocrystals and lead trioxide tetraoxide 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 reducing agentOr/and the molar concentration ratio of the oxidant 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 water₂So as to form carbonic acid solution, and simultaneously react with lead acetate to generate precipitate, 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;

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;

Example 3

(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

(1) 0.1kg (0.1)mol) lead citrate into 1kg of water, and then continuously introducing 0.0005kg (0.01mol) of CO into the water₂Forming 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;

Example 5

(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

(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

(1) 0.1kg of waste lead acid battery lead paste (molar content of Pb of 0.33mol, estimated by a mixed molar mass of 300g/mol) 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 1.25 × 10 g of 1.25 g 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

(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

(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

(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

(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;

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

1. A method for preparing Pb oxide nano powder, the said method can be used for lead-acid battery recovery and manufacturing, including the step:

(1) reacting waste lead-acid storage battery lead paste with an organic or inorganic compound capable of complexing Pb atoms/ions;

the organic or inorganic compound capable of complexing Pb atoms/ions includes: carbon dioxide or carbonic acid and salts thereof;

a reducing agent or/and an oxidizing agent is/are also added into the reaction system in the step (1);

(2) carrying out the treatment processes of filtering, drying to remove water and heating decomposition to obtain Pb oxide nano powder;

in the step (2), the heating temperature range is below 800 ℃.

2. The method of claim 1, wherein: in the step (1), the molar concentration ratio of the organic or inorganic compound capable of complexing Pb atoms/ions is as follows: pb atoms/ions, the ratio of the compound to the Pb atoms/ions is 1: 0.1-1: 1000;

the temperature range of the reaction in the step (1) is below 1000 ℃.

3. The method of claim 1, wherein: formic acid, acetic acid, propionic acid, oxalic acid, malonic acid, lactic acid, citric acid, maleic acid, ethylenediamine tetraacetic acid, polyacrylic acid, polyacrylate, polymaleic acid, tartaric acid, fumaric acid, phthalic acid, oxalic acid, malic acid, salts of these compounds, and mixtures of these compounds and salts thereof can also be added into the reaction system in the step (1).

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), the reducing agent or/and the oxidizing agent comprises: 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: organic acids, bases, and salts thereof, wherein the organic acids comprise: ethylene diamine tetraacetic acid, 1, 2-diaminopropane-N, N, N ', N' -tetraacetic acid, amino acid, glycolic acid; 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, polyacrylic acid, polymaleic acid, tartaric acid, fumaric acid, phthalic acid, malic acid;

the base comprises: ammonia, ethylenediamine, tetramethylammonium hydroxide.

9. The method of claim 1, wherein: 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.

11. The method of claim 1, wherein: the organic or inorganic compound capable of complexing Pb atoms/ions includes: urea.