CN1830805A - Method of preparing tribasic lead sulphate utilizing spent lead battery plate grid and connecting piece - Google Patents
Method of preparing tribasic lead sulphate utilizing spent lead battery plate grid and connecting piece Download PDFInfo
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- CN1830805A CN1830805A CN 200610031387 CN200610031387A CN1830805A CN 1830805 A CN1830805 A CN 1830805A CN 200610031387 CN200610031387 CN 200610031387 CN 200610031387 A CN200610031387 A CN 200610031387A CN 1830805 A CN1830805 A CN 1830805A
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Abstract
A process for preparing lead trihydroxy sulfate from the grate plates and terminals of used lead accumulator includes such steps as cleaning, smelting, quickly pouring the molten lead in cold water to form porous lead, reacting on diluted nitric acid to obtain lead nitrate solution, reacting on sulfuric acid to obtain the deposit of pure lead sulfate, reacting on sodium hydroxide, filtering, drying and pulverizing.
Description
Technical Field
The invention relates to a method for preparing tribasic lead sulfate by using a grid and a connecting piece of a waste lead storage battery.
Background
Lead is widely used in various aspects of national economy as a main metal raw material. China is the country with the fastest increase of lead production and consumption since the last 90 years, but the growing part is almost original lead, while the increase speed of the yield of secondary lead is slower, and the problem of safety guarantee of lead resources becomes a problem which needs to be considered and solved urgently. The development of the lead regeneration industry can fully utilize lead waste, reduce the exploitation amount of primary lead ores, reduce the pollution of the lead waste to the environment and the waste of resources, and lead metal enters the virtuous cycle of production, consumption and regeneration, thereby being an indispensable important component for realizing the sustainable development strategy and the development of circular economy of the lead industry in China.
The industry of the regenerated lead has made remarkable progress in recent 10 years, but from the general level, the existing regenerated lead factory of the waste lead storage battery mainly adopts the traditional smelting processes of a small reverberatory furnace, a blast furnace, a cupola furnace and the like, and the grid and the lead mud are mixed together without pretreatment process basically; some small enterprises and individual households even adopt the original earth kiln for smelting; the problems of large number of enterprises, small scale, high energy consumption, serious pollution, backward industrial technology, low metal recovery rate and comprehensive utilization rate and the like exist.
Tribasic lead sulfate (3 PbO. PbSO)4·H2O) is white or slightly reddish or slightly yellowish powder, has a specific gravity of 7.10, a melting point of 820 ℃, is sweet, toxic, easy to absorb moisture, non-combustible and insoluble in H2O and CH3CH2OH, but dissolved in acid and hot ammonium acetate, is readily discolored and spontaneously decomposed when wet. Lead sulfate tribasic is an important chemical raw material, and the market demand is extremely large. Lead sulfate tribasic has excellent heat resistance, light resistance and electrical insulation properties, and is particularly suitable for high-temperature processing. The product is mainly used as a heat stabilizer and a colorant for opaque polyvinyl chloride hard pipes, plates, injection molding products, rubber and artificial leather products and the like. Because of its excellent insulating property, it is also widely used for polyvinyl chloride electric insulating materials. It can also be used as the color of paint, and has the advantages of light stability and no discoloration.
Because tribasic lead sulfate is an important chemical raw material, the market demand is extremely large. There are three main methods for producing tribasic lead sulfate at home and abroad.
Firstly, a metal lead ingot is used as a raw material and is produced by adopting an oxidation process. The production process comprises the following steps:
lead ingot → molten lead → powdering → oxidation → pulverization → addition of acid (acetic acid, sulfuric acid) reaction → press filtration → drying → pulverization → product
The main chemical reaction formula is: 。
secondly, lead smelting clinker is utilized, and the process flow is as follows: lead clinker → ammonium bicarbonate conversion → fluorosilicic acid leaching → sulfuric acid precipitation → sodium hydroxide synthesis.
Thirdly, adopting a nitric acid method to prepare tribasic lead sulfate from the electrolytic lead slag and lead dross, reacting the electrolytic lead slag and lead dross with nitric acid to generate lead nitrate solution, reacting the lead nitrate solution with sulfuric acid to obtain lead sulfate precipitate, and then adding sodium hydroxide to alkalize the lead sulfate precipitate to obtain the tribasic lead sulfate.
The production process of the tribasic lead sulfate takes lead and lead oxide as raw materials for processing and production. The grid and the lead mud are mixed together to produce the lead ingot, and the lead recovery rate is low in the process of producing various lead compounds from the lead ingot, the process flow is long, resources and energy are seriously wasted, and serious environmental pollution is caused.
Disclosure of Invention
The invention aims to solve the technical problem in the prior art and provides a novel method for producing tribasic lead sulfate by using grids and connecting pieces in waste lead storage batteries, which has the advantages of short process, high metal recovery rate and comprehensive utilization rate, lead resource saving, and environmental pollution and energy consumption reduction.
The technical scheme of the invention is as follows: melting the sorted and cleaned waste lead storage battery grid and the binding post to form lead water, and quickly pouring the lead water into cold water to form the foamed lead with larger specific surface area and more pores; the lead in the foam is reacted with dilute nitric acid to produce lead nitrate solution; reacting the lead nitrate solution with sulfuric acid to produce pure lead sulfate precipitate; finally, lead sulfate reacts with caustic soda solution to synthesize tribasic lead sulfate; and filtering, drying, crushing and packaging to obtain a superior product meeting the requirements of the industrial standard HG 2340-92.
The specific process steps of the invention are as follows:
(1) preparing the pickled lead: the waste lead storage battery is crushed and sorted to separate grid metal and connecting piece metal, and the grid and the connecting piece contain more than 99% of metal lead. After the grid and the connecting piece are cleaned by water, melting at 400-500 ℃ to form lead water; rapidly pouring lead water into the stirred cold water, thereby forming the foam lead with larger specific surface area and more pores; the precipitate was filtered and separated to obtain solid paulownia (residue a).
The filtrate (liquid A) is filtered and naturally cooled for reuse.
(2) Preparation of lead nitrate solution: at normal temperature and normal pressure, according to the ratio of Pb to HNO3Mixing the lead in the foam and 10-15% of dilute HNO (molar ratio) 3: 8.53The solution reacts at a stirring speed of 80r/min for 60 min. The chemical reaction formula is as follows:
filtering after the reaction to obtain relatively pure Pb (NO)3)2Solution (liquid B).
The filter residue (slag B) can enter a blast furnace smelting system together with lead slime for mixing.
(3) Preparing and purifying lead sulfate: the lead nitrate solution obtained in the second step is mixed with 50% sulfuric acid in terms of Pb (NO)3)2∶H2SO4The reaction is carried out according to the molar ratio of 1: 1.05 to obtain lead sulfate precipitate. The reaction conditions are normal temperature and normal pressure, and the stirring is carried out for 30min at the speed of 80 r/min. The chemical reaction formula is as follows:
cleaning the filter residue to obtain purified PbSO4Solid (slag C). The filtrate is HNO3Solution (liquid C), collecting and supplementing appropriate amount of HNO3And then the lead nitrate solution is recycled and used for preparing the lead nitrate solution in the second step of reaction.
(4) Tribasic lead sulfate (3 PbO. PbSO)4·H2O) synthesis: purified PbSO4Mixing the solid with 10-20% NaOH solution according to PbSO4NaOH is reacted for 60min at normal temperature and pressure with the molar ratio of 1: 1.06, and the stirring speed is 80 r/min. Standing to obtain white tribasic lead sulfate precipitate. The chemical reaction formula is as follows:
and (3) after precipitation and filtration, washing filter residues to be neutral (the pH value is 6.5-7.5), drying for 90-120 min at 105-110 ℃, crushing and packaging to obtain a qualified product.
The lead sulfate tribasic produced by theprocess for the grid and the connecting piece of the waste lead storage battery meets the first-grade standard in HG2340-92 standards, and the PbO content is more than 89%. The lead recovery rate of the process is more than 99 percent, the lead resource can be greatly saved, the high-efficiency recovery of the grid and the connecting piece of the waste lead storage battery is realized, the process generates tribasic lead sulfate by preparing the foamed lead as the raw material, and the reaction speed is greatly improved compared with that of lead powder as the raw material; the process flow is short, the energy can be saved, the environmental pollution is reduced, a new way is opened for the recycling of lead resources, and the principle of recycling economy is met.
Drawings
Fig. 1 is a process flow diagram of the new method for preparing tribasic lead sulfate by using the grid and the connecting piece of the waste lead storage battery.
Detailed Description
The process is further illustrated below with reference to specific examples of implementation:
example 1 referring to fig. 1, the first step, preparation of bubbled lead, slab lattice sorted from scrap lead storage batteryCleaning the metal and the metal of the connecting piece with water; melting the cleaned grid and binding post metal 239g into lead water in a 200ml copper crucible furnace, wherein the melting temperature is 400 ℃; pouring molten lead into cold water under stirring quickly to form the foamed lead with larger specific surface area and more pores, and filtering and separating to obtain solid foamed lead (residue A); filtering the filtrate (liquid A), naturally cooling and reusing; the second step, preparation of lead nitrate solution, mixing the steep lead obtained in the first step with 2065g of 10% HNO3The solution reacts in a reactor under the conditions of normal temperature and normal pressure, the stirring speed is 80r/min, and the reaction time is 60 min; then filtering to obtain relatively pure Pb (NO)3)2Solution (liquid B); thirdly, preparation and purification of lead sulfateReacting the lead nitrate solution obtained in the second step with 235g of 50% sulfuric acid in a reactor to produce lead sulfate precipitate, wherein the reaction conditions are normal temperature and normal pressure, the stirring speed is 80r/min, and the reaction time is 30 min; cleaning the filter residue to obtain purified PbSO4About 344g of solids (slag C); the filtrate is HNO3Solution (liquid C), collecting and supplementing appropriate amount of HNO3Then the lead nitrate solution is recycled and used for preparing the lead nitrate solution in the second step of reaction; step four, 3 PbO. PbSO4·H2O synthesis, and the PbSO obtained in the third step4Reacting the solid with 480g of 15 percent NaOH solution at normal temperature and normal pressure for 60min, wherein the stirring speed is 80 r/min; after the reaction is finished, washing to be neutral (the pH value is about 7), drying for 90-120 min at 105-110 ℃, crushing and packaging to obtain 275g of qualified product. The PbO content in the product is 89.9 percent, which meets the first-level standard in the national HG2340-92 standard.
Example 2 grid and lug metal 253g, other chemicals were mixed in the same proportions and the second step HNO adjusted as described in example 13The concentration of the solution is 15 percent (1457g), the concentration of the NaOH solution in the fourth step is 20 percent (380g), about 290g of qualified tribasic lead sulfate product is obtained, and the content of PbO in theproduct is 89.5 percent.
Example 3. Using the same method and procedure as in example 1, an expanded experiment was conducted to produce about 12.00kg of acceptable tribasic lead sulfate product with a PbO content of 89.7% using 10.52kg of waste lead storage battery grids and connectors at a time and other chemicals in the same proportions.
Claims (2)
1. A method for preparing tribasic lead sulfate by utilizing waste lead storage battery grids and connecting pieces is characterized by comprising the following steps: melting the sorted and cleaned waste lead storage battery grid and the binding post to form lead water, and quickly pouring the lead water into cold water to form the foamed lead with larger specific surface area and more pores; the lead in the foam is reacted with dilute nitric acid to produce lead nitrate solution; reacting the lead nitrate solution with sulfuric acid to produce pure lead sulfate precipitate; finally, lead sulfate reacts with caustic soda solution to synthesize tribasic lead sulfate; and filtering, drying, crushing and packaging to obtain a superior product meeting the requirements of the industrial standard HG 2340-92.
2. The method of using waste lead storage battery grids and connectors to produce tribasic lead sulfate according to claim 1, wherein: the process comprises the following steps:
(1) preparing the pickled lead: crushing and sorting the waste lead storage battery, separating out grid metal and connecting piece metal, wherein the grid and the connecting piece contain more than 99% of metal lead, and the grid and the connecting piece are melted at 400-500 ℃ to form lead water after being washed by water; quickly pouring lead water into the stirred cold water to form the foamed lead withlarger specific surface area and more pores; precipitating, filtering and separating to obtain solid pickled lead, and naturally cooling the filtered filtrate for reuse;
(2) preparation of lead nitrate solution: at normal temperature and normal pressure, according to the molar ratio of Pb to HNO3Soaking lead and 10-15% of dilute HNO (sodium hydroxide) at a ratio of 3: 8.53Reacting the solution, wherein the stirring speed is 80r/min, the reaction time is 60min, filtering is carried out after the reaction to obtain a relatively pure lead nitrate solution, and the filter residue and the lead mud enter a blast furnace smelting system together for mixing;
(3) preparing and purifying lead sulfate: the lead nitrate solution obtained in the second step is mixed with 50 percent sulfuric acid according to the molar ratio of Pb (NO)3)2∶H2SO4Reacting at the ratio of 1: 1.05 to obtain lead sulfate precipitate, and reactingStirring at 80r/min for 30min under normal temperature and pressure, cleaning the residue to obtain purified lead sulfate solid, and filtering to obtain HNO filtrate3Collecting and supplementing appropriate amount of HNO3Then the lead nitrate solution is recycled and used for preparing the lead nitrate solution in the second step of reaction;
(4) synthesis of tribasic lead sulfate: mixing the purified lead sulfate solid with 10-20% NaOH solution according to the molar ratio of PbSO4Reacting NaOH at the ratio of 1: 1.06 for 60min at normal temperature and pressure, stirring at the speed of 80r/min, standing to obtain white tribasic lead sulfate precipitate, filtering the precipitate, washing filter residue to be neutral, controlling the pH value to be 6.5-7.5, drying at 105-110 ℃ for 90-120 min, crushing, and packaging to obtain the qualified product.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101899573A (en) * | 2010-07-22 | 2010-12-01 | 中国电子工程设计院 | Method for processing lead-acid accumulators |
| CN101924218A (en) * | 2010-09-08 | 2010-12-22 | 江苏理士电池有限公司 | Process for manufacturing lead-acid battery grid |
| CN110656246A (en) * | 2019-09-27 | 2020-01-07 | 安徽华铂再生资源科技有限公司 | Disassembling processing technology based on waste storage battery |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1202461A (en) * | 1997-06-13 | 1998-12-23 | 烟台鹏晖铜业有限公司 | Process for producing three basic lead sulphate using lead in copper slime |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101899573A (en) * | 2010-07-22 | 2010-12-01 | 中国电子工程设计院 | Method for processing lead-acid accumulators |
| CN101899573B (en) * | 2010-07-22 | 2013-09-25 | 中国电子工程设计院 | Method for processing lead-acid accumulators |
| CN101924218A (en) * | 2010-09-08 | 2010-12-22 | 江苏理士电池有限公司 | Process for manufacturing lead-acid battery grid |
| CN110656246A (en) * | 2019-09-27 | 2020-01-07 | 安徽华铂再生资源科技有限公司 | Disassembling processing technology based on waste storage battery |
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