阅读说明：本技术 一种废铅膏回收处理方法 (Waste lead paste recovery treatment method ) 是由 代少振 陈幸 项晨 于 2019-09-18 设计创作，主要内容包括：本发明涉及一种废铅膏回收处理方法,包括第一步,废铅膏分离出滤渣和滤液；第二步,废铅膏分离滤液提纯；第三步,废铅膏分离滤渣提纯。本发明还保护了一种废旧铅酸蓄电池循环回收方法。本发明的回收处理方法,高效、环保。(The invention relates to a waste lead plaster recycling method, which comprises the first step of separating filter residue and filtrate from waste lead plaster; secondly, separating and purifying the waste lead paste filtrate; and thirdly, separating and purifying the waste lead paste and filter residue. The invention also provides a recycling method of the waste lead-acid storage battery. The recovery processing method of the invention is high-efficient and environment-friendly.)

1. A method for recycling and treating waste lead paste comprises the first step of separating filter residue and filtrate from the waste lead paste; secondly, separating and purifying the waste lead paste filtrate; and thirdly, separating and purifying the waste lead paste and filter residue.

2. The method for recycling and treating the waste lead plaster as claimed in claim 2, wherein the purification of the separation and filtration residue of the waste lead plaster comprises the following steps of 1: stirring and mixing the filter residue separated in the first step and a sodium chloride solution in an enamel reaction kettle for reaction, completely dissolving lead sulfate in the filter residue, filtering and centrifugally separating the dissolved materials to obtain filter residue and filtrate, circularly dissolving the filter residue for reuse, cooling and crystallizing the filtrate, centrifugally separating and collecting lead chloride crystals and filtrate, treating the filtrate, and reducing the lead chloride crystals into metallic lead and hydrogen chloride gas after the lead chloride crystals are put into a reduction furnace.

3. The method for recycling and treating waste lead paste according to claim 2, wherein the hydrogen chloride gas in step 1 is recycled and reused for absorption by the hydrochloric acid and sodium chloride filtrate dissolved and filtered in the first step.

4. The method for recycling and treating the waste lead plaster as claimed in claim 2, wherein the purification of the separation and filtration residue of the waste lead plaster further comprises the following steps of 2: and (3) adding the filtrate obtained by filtering and centrifuging the dissolved materials in the step (1) into calcium chloride, stirring and reacting, filtering and separating sodium chloride filtrate and calcium sulfate slag after the reaction is completed, recycling the sodium chloride filtrate, and recovering the calcium sulfate slag for later use.

5. The method for recycling waste lead paste as claimed in claim 4, wherein the sodium chloride filtrate is used for continuous dissolution and reuse in the same manner as the filter residue used for continuous dissolution and reuse in step 1.

6. A method for recycling waste lead-acid storage batteries comprises the following steps of (1) serially connecting waste batteries for charging; (2) punching and acid pouring treatment of the waste lead-acid battery; (3) crushing and sorting waste batteries; (4) recycling the plastic shell and the partition board paper; (5) recovering and treating the grid and the lead pieces; (6) the method for recycling and treating waste lead paste according to any one of claims 1 to 5.

Technical Field

The invention relates to the field of lead-acid storage batteries.

Background

The lead-acid battery is closely related to the development of the industries of the national civilization, such as electric power, traffic, information and the like, and is an indispensable product for social production and operation and human life. With the rapid development of the fields of related electric power-assisted vehicles, electric tricycles, electric automobiles, energy storage communication, electric power and the like, lead-acid storage batteries still grow continuously, so that the recycling of a large number of scrapped batteries becomes a huge social problem, the scrapping period of the lead-acid storage batteries due to corrosion, passivation and the like is generally 3-5 years, the number of scrapped lead storage batteries replaced from vehicles, ships and communication base stations in China every year in recent years is huge, the scrapped batteries not only waste resources seriously, but also can cause serious threats to the ecological environment and the human health. The basic raw materials for manufacturing the lead-acid storage battery are metallic lead and sulfuric acid, and along with the scrapping of the lead-acid storage battery, a large amount of lead-containing waste in the battery needs to be treated. Lead is a metal harmful to the environment and human health, and various lead wastes can cause great harm to the environment and human body if not reasonably recycled, and particularly, the environment pollution caused by lead plaster and sulfuric acid in the waste lead storage batteries can be avoided only by fully recycling the waste lead storage batteries.

Disclosure of Invention

In order to solve the technical problem, the invention provides a waste lead paste recovery processing method, which comprises the first step of separating filter residue and filtrate from waste lead paste; secondly, separating and purifying the waste lead paste filtrate; and thirdly, separating and purifying the waste lead paste and filter residue.

Further, the waste lead plaster separation and filter residue purification comprises the following steps of 1: stirring and mixing the filter residue separated in the first step and a sodium chloride solution in an enamel reaction kettle for reaction, completely dissolving lead sulfate in the filter residue, filtering and centrifugally separating the dissolved materials to obtain filter residue and filtrate, circularly dissolving the filter residue for reuse, cooling and crystallizing the filtrate, centrifugally separating and collecting lead chloride crystals and filtrate, treating the filtrate, and reducing the lead chloride crystals into metallic lead and hydrogen chloride gas after the lead chloride crystals are put into a reduction furnace.

Further, the hydrogen chloride gas in the step 1 is circularly applied and absorbed by the hydrochloric acid and the sodium chloride filtrate after being dissolved and filtered in the first step.

Further, the purification of the waste lead paste separation filter residue also comprises a step 2: and (3) adding the filtrate obtained by filtering and centrifuging the dissolved materials in the step (1) into calcium chloride, stirring and reacting, filtering and separating sodium chloride filtrate and calcium sulfate slag after the reaction is completed, recycling the sodium chloride filtrate, and recovering the calcium sulfate slag for later use.

Further, the sodium chloride filtrate and the filter residue for continuous dissolution and reuse in the step 1 are continuously dissolved and reused in the same manner.

The invention also provides a recycling method of the waste lead-acid storage battery.

The recovery processing method is efficient and environment-friendly.

Drawings

FIG. 1 is a flow chart of the recovery of a waste lead acid storage battery according to the present invention;

fig. 2 is a flow chart of the recycling of the waste lead paste of fig. 1.

Detailed Description

Referring to fig. 1, the recycling process of the waste lead-acid storage battery of the present invention comprises the following steps:

(1) waste battery series charging

The waste lead-acid storage battery is charged in series for 8-12h according to the current limit of 0.15C of 14.7V/battery.

(2) Waste lead-acid battery punching and acid pouring treatment

And punching the fully charged waste lead acid storage battery cover, pouring acid liquor in the waste lead acid storage battery out for centralized collection after punching, and directly using the collected waste acid for preparation of battery formation acid after filtering and impurity removal.

(3) Crushing and sorting waste batteries

The waste lead-acid storage battery is crushed by a crusher and then separated into lead plaster, lead pieces, grids, plastic shells and AGM partition paper by a gravity flotation method. And the plastic shell and the partition board paper are recycled and sold to plastic shell manufacturers and partition board paper manufacturers after being washed.

(4) Plastic shell and partition paper recovery treatment

The plastic shell and the partition board paper are washed clean by using natural water and then sold to plastic shell manufacturers and partition board paper manufacturers, and the prepared plastic shell and the partition board paper are recycled.

(5) Recovery treatment of slab lattice and lead parts

And (3) smelting the grid and the lead piece in the step (2) in a smelting furnace at low temperature to prepare the alloy lead used for the lead-acid battery. The smelting temperature is controlled at 500-800 ℃.

(6) Waste lead paste recovery treatment

Firstly, separating waste lead paste.

Preparing a mixed solution of hydrochloric acid (1% -5%) and sodium chloride with the concentration (15% -30%), mixing the waste lead plaster with the mixed solution of hydrochloric acid and sodium chloride according to the mass ratio of 1 (3-5), putting the mixture into an enamel reaction kettle, heating to 70-100 ℃, quickly stirring, mixing and reacting for 2-5 hours, sampling and analyzing the reaction process, titrating and monitoring the dissolution degree of lead ions in the reaction process by using EDTA (ethylene diamine tetraacetic acid), and finishing the reaction when the dissolution of the lead ions is not increased any more. The dissolution process takes place as follows. The reaction equation is as follows:

PbO+2HCl→Pb^Cl2+H2O；PbO2+Pb+4HCl→2PbCl2+2H2O

and secondly, separating and purifying the waste lead paste filtrate.

And (3) after the reaction is finished, carrying out centrifugal separation and filtration while the reaction is hot, keeping filter residues for later use, cooling, crystallizing, carrying out centrifugal separation on the filtrate to separate out lead chloride crystals, carrying out centrifugal separation to collect lead chloride, and recycling the filtrate. Putting the lead chloride crystals obtained by centrifugal separation into a reduction furnace, heating to 100-DEG C and 150-DEG C to evaporate water, stopping heating, slowly introducing hydrogen to replace water vapor and air in the reduction furnace, repeatedly replacing for three times, introducing hydrogen, continuously heating to 400-DEG C and 600-DEG C to reduce the lead chloride into metallic lead, and reacting as follows:

the reaction equation is as follows: PbCl2+ H2 → Pb +2HCl ↓ ≠

In the second step, the byproduct hydrogen chloride gas generated by the reaction is circularly applied and absorbed by the hydrochloric acid and the sodium chloride filtrate which are dissolved and filtered in the first step. The absorption liquid is used for dissolving and purifying lead, lead dioxide and lead oxide in the lead plaster.

And thirdly, separating and purifying the waste lead paste and filter residue.

Step 1, sampling the filter residue separated in the first step to detect the content of lead sulfate, then stirring and mixing the filter residue and a (10% -20%) sodium chloride solution in a mass ratio (1: 3) in an enamel reaction kettle at 70-100 ℃ for reaction according to the net weight of the filter residue of lead sulfate calculated by the content of lead sulfate, and completely dissolving the lead sulfate in the filter residue. The dissolution of the filter residue takes place as follows. The reaction equation is as follows: PbSO4+2NaCl → PbCl2+ Na2SO4

Filtering and centrifuging the dissolved materials, and circularly dissolving and recycling filter residues. Cooling and crystallizing the filtrate to completely separate out lead chloride crystals, then centrifugally separating and collecting the lead chloride crystals, and treating the filtrate. Putting the lead chloride crystal into a reduction furnace, heating to 100-150 ℃ to evaporate water, stopping heating, slowly introducing hydrogen to replace water vapor and air in the reduction furnace, repeatedly replacing for three times, introducing hydrogen, continuously heating to (400-600) ℃ while continuously heating, and reducing the lead chloride into metallic lead. The reaction is as follows: the reaction equation is as follows: PbCl2+ H2 → Pb +2HCl ↓ ≠

And (3) circularly applying the hydrogen chloride gas as a byproduct generated in the step (1) to the hydrochloric acid and the sodium chloride filtrate which are dissolved and filtered in the step (1) for absorption. The absorption liquid is used for dissolving and purifying lead, lead dioxide and lead oxide in the lead plaster.

And 2, adding calcium chloride in a molar ratio of 1 (1-1.1) to the lead sulfate into the filtrate to be treated in the step 1, stirring for reaction, filtering and separating after the reaction is completed, circularly sleeving the filtrate for dissolving lead sulfate and lead slag, and recycling the calcium sulfate slag for later use. The reaction is as follows:

the reaction equation is as follows: na2SO4+ CaCl2 → 2Na^Cl+CaSO4↓

And (4) continuously dissolving the sodium chloride filtrate and the filter residue for continuous dissolving and recycling in the step 1 in the same manner.

The second and third steps of the present invention are preferably performed simultaneously.