CN112607767A - Preparation method of red lead - Google Patents
Preparation method of red lead Download PDFInfo
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- CN112607767A CN112607767A CN202011326988.2A CN202011326988A CN112607767A CN 112607767 A CN112607767 A CN 112607767A CN 202011326988 A CN202011326988 A CN 202011326988A CN 112607767 A CN112607767 A CN 112607767A
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- lead
- carbonate
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- 238000000034 method Methods 0.000 claims abstract description 32
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- 239000004473 Threonine Substances 0.000 description 1
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- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G21/00—Compounds of lead
- C01G21/14—Carbonates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention relates to a preparation method of red lead, which is characterized by comprising the following steps: step 1: desulfurizing the waste lead plaster, and performing solid-liquid separation to obtain a condensate containing lead carbonate; and 2, introducing air into the condensate containing the lead carbonate, carrying out high-temperature smelting to obtain red lead and waste gas, inputting the waste gas into an ammonia water device, and producing the desulfurizing agent containing the ammonia carbonate, wherein the desulfurizing agent containing the ammonia carbonate is used for desulfurizing the waste diachylon in the step 1. The method for preparing the red lead has simple process and high efficiency.
Description
Technical Field
The invention relates to the field of lead-acid storage batteries.
Background
The red lead can accelerate the formation speed and improve the initial discharge capacity of the battery in the formation process of the high-strength polar plate, the red lead is usually required to be added in the preparation method of the anode material of the lead-acid storage battery at present, and the red lead is usually required to be additionally purchased by a user at present and added in the paste mixing process, so that the production cost of the lead-acid storage battery is greatly improved.
Disclosure of Invention
In order to solve the technical problems, the invention provides a method for preparing red lead, which is characterized by comprising the following steps: step 1: desulfurizing the waste lead plaster, and performing solid-liquid separation to obtain a condensate containing lead carbonate; and 2, introducing air into the condensate containing the lead carbonate, carrying out high-temperature smelting to obtain red lead and waste gas, inputting the waste gas into an ammonia water device, and producing the desulfurizing agent containing the ammonia carbonate, wherein the desulfurizing agent containing the ammonia carbonate is used for desulfurizing the waste diachylon in the step 1.
Further, in the step 2, the solidified material containing the lead carbonate is roasted at the temperature of 440-480 ℃ by blowing air to obtain the red lead.
Further, the step 2 is preceded by a step of purifying the lead carbonate-containing solidified substance.
Further, the purification step includes roasting the cured product containing lead carbonate to obtain lead oxide, reacting the lead oxide with a complexing solution to obtain a complex lead solution, introducing carbon dioxide into the complex lead solution to prepare high-purity lead carbonate, wherein the cured product containing lead carbonate in the step 2 is the high-purity lead carbonate.
And further introducing carbon dioxide into the complex lead liquid to prepare a complex liquid, and continuously circulating the complex liquid for purifying the cured product containing the lead carbonate.
Further, a dispersing agent is also added into the complexing liquid.
Further, before the complexing lead liquid is introduced with carbon dioxide to prepare the high-purity lead carbonate, a dispersing agent is also added into the complexing lead liquid.
Further, the waste gas in step 2 comprises carbon dioxide and sulfur dioxide.
Further, in the step 1, ammonia desulphurization is performed on the waste lead plaster, solid-liquid separation is performed to obtain liquid of ammonium sulfate, the liquid of ammonium sulfate reacts with calcium oxide or calcium hydroxide to generate lime and ammonia gas, and the ammonia gas is input into an ammonia water device.
The method for preparing the red lead has simple process and high efficiency.
Drawings
FIG. 1 is a schematic diagram of a lead-acid battery positive electrode material preparation device of the invention.
Detailed Description
The invention is further described below with reference to the specific drawings.
As shown in fig. 1, the lead-acid storage battery positive electrode material preparation device of the present invention includes a roasting device 1, a heat exchanger 2, a gas purification device 3, a tail gas treatment product conversion device 4, a first solid-liquid separation device 5, a gypsum generation device 6, a second solid-liquid separation device 7, a purification device 6a, a lead carbonate preparation device 6b, a purification solid-liquid separation device 7a, and a lead carbonate solid-liquid separation device 7 b. The roasting device 1 comprises a tail gas outlet 8, the tail gas outlet 8 is communicated with an air inlet 9 of a heat exchanger 2, an air outlet 10 of the heat exchanger 2 is communicated with an air inlet 11 of a gas purifying device 3(3a), an air outlet 12 of the gas purifying device 3(3a) is communicated with an inlet 14 of a tail gas treatment product converting device 4, an outlet 15 of the tail gas treatment product converting device 4 is communicated with an inlet 16 of a first solid-liquid separating device 5, an outlet 17 and an outlet 18 of the first solid-liquid separating device 5, the outlet 17 is communicated with an inlet 19 of a gypsum generating device 6, the outlet 18 is communicated with an inlet 20 of the roasting device 1, an air outlet 25 of the gypsum generating device 6 is communicated with the air inlet 11 of the gas purifying device 3, an outlet 21 of the gypsum generating device 6 is communicated with an inlet 22 of a second solid-liquid separating device 7, an outlet 23 of the second solid-liquid separating device 7 is communicated with an inlet, or may communicate with the gas inlet 11 of the gas purification apparatus 3(3 a). The lead-acid storage battery anode material preparation device also comprises a purification system for purifying the condensate containing lead carbonate, the condensate containing lead carbonate separated from the first solid-liquid separation device 5 is conveyed to the roasting device 1, crude lead oxide obtained by the first roasting of the condensate is conveyed to the purification device 6a through a feed inlet 27 of the purification device 6a, a discharge outlet 28 of the purification device 6a is communicated with a feed inlet 29 of the purification solid-liquid separation device, a discharge outlet 30 of the purification solid-liquid separation liquid is communicated with a feed inlet 31 of the high-purity lead carbonate preparation device 6b, a discharge outlet 32 of the high-purity lead carbonate preparation device 6b is connected with a feed inlet 33 of the lead carbonate solid-liquid separation device, a mother liquor discharge outlet 34 of the high-purity lead carbonate solid-liquid separation device is communicated with a feed inlet 37 of the crude lead oxide purification device, a discharge outlet 35 of the, the condensate such as lead oxide prepared by roasting high-purity lead carbonate in the roasting device 1 is sent to a paste mixing device, proper sulfuric acid is added for mixing paste to prepare the positive active substance, and the byproduct carbon dioxide generated by roasting can be communicated with a feed inlet 38 of the high-purity lead carbonate preparation device after passing through a heat exchanger 2 and then recycled for preparing the high-purity lead carbonate.
The preparation method of the lead-acid storage battery anode material comprises the following steps: the method comprises the steps of enabling liquid containing ammonia sulfate and ammonium carbonate in a gas purification device 3 to flow into a tail gas treatment product conversion device 4 through a conveying pipeline, placing waste lead plaster substances containing lead sulfate in the tail gas treatment product conversion device 4, enabling the liquid containing the ammonia sulfate and the ammonium carbonate, namely a sulfur removal agent to flow into the tail gas treatment product conversion device 4 and then to react with the lead sulfate to obtain a solid-liquid mixture containing the ammonia sulfate, the lead carbonate and residual lead sulfate, conveying the solid-liquid mixture to a first solid-liquid separation device 5, conveying the separated liquid ammonia sulfate into a gypsum generation device 6, enabling the gypsum generation device 6 to contain a mixture of calcium oxide and water or calcium hydroxide, conveying the separated liquid ammonia sulfate into the gypsum generation device 6, reacting to obtain calcium sulfate (common name gypsum) and ammonia water or ammonia water and ammonia gas, conveying the obtained calcium sulfate and ammonia water to a second solid-liquid separation device 7, the obtained calcium sulfate was washed and sold as a raw material. In order to ensure that sufficient carbon dioxide or sulphur dioxide is removed from the off-gas to ultimately produce as much gypsum as possible, the resulting ammonia gas is preferably also fed to the gas cleaning device 3. The solid containing lead carbonate and lead sulfate separated by the first solid-liquid separator 5 is conveyed into the smelting device 1 to be roasted by the following steps: 1) roasting the mixture for 1 to 5 hours at the temperature of 315 plus 486 ℃ in an air-isolated manner to generate alpha-lead oxide; 2) the mixture of beta lead oxide and alpha lead oxide with the proportion of 5 percent to 25 percent is obtained after the subsequent temperature generation is 500-580 ℃ and the mixture is roasted for 5 to 30 min; 3) then the mixed material is roasted for 1 to 3 hours at the temperature of 440-480 ℃ and air is blown into the mixed material to obtain a mixture of the red lead content (5 to 25 percent), the beta lead oxide content (5 to 25 percent) and the balance of alpha lead oxide; 4) mixing the paste; mixing the lead powder mixture, conductive fiber and positive battery additive according to a certain proportion, putting the mixture into a paste mixing device for dry mixing for 5-10min, quickly adding 10-12% of pure water for wet mixing for 5-10min after the dry mixing is finished, adding 7-9% of paste mixing acid with the density of 1.40g/ml within 10-20min after the mixing is finished, continuously mixing for 5-10min after the adding is finished, cooling to below 45 ℃, detecting that the lead paste is qualified according to specific gravity, and discharging the coated plate. The temperature of the mixed paste is not more than 70 ℃ in the acid adding process of the mixed paste, and the mixed paste is stable at 65-70 ℃ for 3-5min in the acid adding process. The corresponding alpha-lead oxide, beta-lead oxide and red lead are obtained by controlling the roasting temperature and the amount of air. The solid containing lead carbonate and lead sulfate separated by the first solid-liquid separation device 5 can also be conveyed into the smelting device 1 in batches for roasting, and a part of condensate is smelted to a first temperature at a high temperature to obtain alpha-lead oxide which is taken out; then, melting a part of condensate containing the lead carbonate at a high temperature to a second temperature, introducing oxygen to obtain lead tetraoxide, namely red lead, and taking out; and (3) melting a part of condensate containing the lead carbonate to a third temperature at a high temperature to obtain beta lead oxide, and taking out the beta lead oxide. Thereby producing the alpha-lead oxide, the beta-lead oxide and the red lead separately, and better preparing the mixture ratio among the alpha-lead oxide, the beta-lead oxide and the red lead.
In the positive lead plaster, alpha lead oxide can quickly react with sulfuric acid in the curing process to generate lead sulfate, then redundant alpha lead oxide is combined with the lead sulfate to generate a large number of 3BS (3-base sulfide) net structures, and meanwhile, beta lead oxide generated after 3BS is quickly combined with part of 3BS to quickly generate a large number of 4BS (4-base sulfide) to improve the self of positive active substances and the bonding strength with a grid and improve the cycle service life and the electrochemical performance of the battery. The red lead can accelerate the formation speed and improve the initial discharge capacity of the battery in the formation process of the high-strength polar plate.
The preparation of the positive electrode material also comprises the steps of purifying and refining the condensate containing the lead carbonate. The solidified material containing lead carbonate and lead sulfate separated by the first solid-liquid separator 5 is conveyed to the smelting device 1 to be roasted to obtain lead oxide, and the lead oxide can be alpha lead oxide. The lead oxide enters a purification device 6a to react with the complexing liquid for purification, and the reaction is as follows: FbO + R + H2O → PbR2++2OH-. R is a food-grade dissolving and purifying complexing agent, and the complexing agent is generally: triethylamine, ethylenediamine, acetic acid, tartaric acid, oxalic acid, aspartic acid, alanine, sarcosine, phenylalanine, leucine, histidine, asparagine, glycine, threonine and acetic acid, wherein the dispersant is one or more of polyvinylpyrrolidone, polyvinyl alcohol, sodium carboxymethylcellulose and sodium dodecyl benzene sulfonate. The purified complex lead liquid is separated by a solid-liquid separation device 7a to obtain high-purity complex lead liquid and a small amount of solid lead slag, the lead slag and the desulfurized waste lead plaster are continuously mixed, desulfurized and roasted to prepare crude lead oxide, the complex lead liquid enters a high-purity lead carbonate preparation device 6b, carbon dioxide is added to prepare high-purity lead carbonate, and the lead carbonate is separated by the solid-liquid separation device 7b to obtain complex liquid and high-purity lead carbonate, wherein the reaction is as follows: PbR2++2OH-+ CO2 → PbCO3 ↓ + R + H2O, the complex liquid enters the purification device 6a to continue to circulate for the purification of crude lead oxide, the high purity lead carbonate enters the roasting device 1 to prepare alpha lead oxide, beta lead oxide and lead tetroxide according to the above process steps. In order to achieve finer lead oxide and thus achieve better effect of preparing the cathode material, a dispersant, such as polyvinylpyrrolidone, may be added to at least one of the purification apparatus 6a and the high purity lead carbonate preparation apparatus 6b, the dispersant may enable the lead oxide to form nano-particles, the dispersant may be added to perform a reaction in an ultrasonic state to achieve better effect, and the dispersant is added to the high purity lead carbonate preparation apparatus 6b and then carbon dioxide is passed through. So that the prepared high-purity nano-scale lead carbonate enters the roasting device 1 to prepare nano alpha lead oxide, nano beta lead oxide and nano lead tetraoxide.
And (2) conveying the waste gas of the gas containing carbon dioxide and sulfur dioxide obtained by roasting in the roasting device 1 into the heat exchanger 2 through a pipeline for cooling treatment, wherein one part of the cooled waste gas is used for preparing high-purity lead carbonate, and the other part of the cooled waste gas is conveyed into the gas purification device 3 with ammonia water stored through a pipeline to obtain liquid containing ammonium sulfate and ammonium carbonate, and the liquid containing the ammonium sulfate and the ammonium carbonate is used for desulfurization and recycling of the waste lead plaster.
According to the preparation method of the lead-acid storage battery anode material, the product obtained after the waste lead plaster is desulfurized is smelted to directly obtain the paste mixing material, so that on one hand, the preparation efficiency of the anode material is greatly improved, and on the other hand, the lead plaster desulphurization, the smelting tail gas recovery and the preparation of the anode material form an organic complete system.
The gas purification device 3 of the invention is preferably an ammonia process gas purification device, which comprises a primary ammonia water spray tower 3a and can also comprise a secondary spray tower 3b, wherein the primary ammonia water spray tower 3a can overflow from the top of the primary ammonia water spray tower 3a if a small amount of incompletely absorbed gas exists, and the incompletely absorbed gas is conveyed to the secondary spray tower 3b through a pipeline to be absorbed by ammonia water to prepare an amine carbonate or ammonium bicarbonate solution, and the amine carbonate or ammonium bicarbonate solution is conveyed to a tail gas treatment product conversion device 4 after meeting the requirement on the solubility of the amine carbonate or ammonium bicarbonate, so that the gas in the tail gas can be fully absorbed, and gypsum can be finally formed as much as possible. The solid-liquid separator of the present invention can perform solid-liquid separation by using an appropriate method such as a scraper method or a centrifugal method. The invention may also include a washing device for washing the calcium sulfate solid precipitate for later use. In order to ensure that the ammonia process gas purification device can obtain ammonia sulfate as much as possible after absorbing tail gas and further obtain gypsum as much as possible subsequently, hydrogen peroxide can be added into the ammonia process gas purification device to convert sulfite ions into sulfate ions to form ammonia sulfate. In addition, an oxygen blowing port may be provided at the gypsum production apparatus 6 to convert calcium sulfite, which may be generated at the gypsum production apparatus 6, into calcium sulfate by blowing oxygen. It is also possible to add hydrogen peroxide and oxygen blowing at the same time.
In addition, the present invention can also purify a lead sulfate-containing cured product by the same purification method.
The method of the invention can also prepare only red lead according to the requirement, as long as the corresponding temperature and the amount of air introduced are controlled. Namely, air is introduced into the condensate containing the lead carbonate, high-temperature smelting is carried out, and air is blown into the condensate at the temperature of 440-480 ℃ for roasting to obtain red lead, red lead and waste gas are obtained, and the red lead is reserved. The other ways are the same. The invention prepares the red lead by the product of the waste lead plaster after desulfurization, and simultaneously recycles the generated waste gas for preparing the desulfurizer and the gypsum to form a complete self-circulation system.
The method of the present invention can also prepare only lead oxide as required, as long as the corresponding temperature is controlled and air is excluded. Namely, the solidified material containing the lead carbonate is baked at the temperature of 315-486 ℃ without air to generate alpha-lead oxide; then heating to 500-580 ℃ to bake the obtained mixture of the beta lead oxide and the alpha lead oxide. The other ways are the same. According to the invention, the lead oxide is prepared from the product of waste lead plaster after desulfurization, and the generated waste gas is recycled for preparing the desulfurizer and the gypsum, so that a complete self-circulation system is formed. In addition, the process from crude lead to refined lead is not needed, and the production cost is greatly reduced.
The method can also be used for further preparing 4BS together with dilute sulfuric acid according to the prepared alpha lead oxide and beta lead oxide, wherein the alpha lead oxide quickly reacts with the sulfuric acid to generate lead sulfate, then redundant alpha lead oxide is combined with the lead sulfate to generate a 3BS large-amount 3BS reticular structure, and meanwhile, the beta lead oxide quickly combines with part of 3BS to generate a large amount of 4BS after the 3BS is generated. 4BS improves the bonding strength of the positive active material and the grid, and improves the cycle service life and the electrochemical performance of the battery.
The desulfurizing agent of the present invention may be a liquid containing only ammonium sulfate or ammonium carbonate or a mixed liquid thereof.
The above-described embodiments are only preferred embodiments of the present invention, and are not intended to limit the present invention in any way, and other variations and modifications may be made without departing from the spirit of the invention as set forth in the claims.
Claims (9)
1. The preparation method of the red lead is characterized by comprising the following steps: step 1: desulfurizing the waste lead plaster, and performing solid-liquid separation to obtain a condensate containing lead carbonate; and 2, introducing air into the condensate containing the lead carbonate, carrying out high-temperature smelting to obtain red lead and waste gas, inputting the waste gas into an ammonia water device, and producing the desulfurizing agent containing the ammonia carbonate, wherein the desulfurizing agent containing the ammonia carbonate is used for desulfurizing the waste diachylon in the step 1.
2. The method as claimed in claim 1, wherein in step 2, the solidified material containing lead carbonate is baked at 440-480 ℃ with air blowing to obtain red lead.
3. The method according to claim 1, wherein the step 2 is preceded by a step of purifying the cured product containing lead carbonate.
4. The method for preparing red lead according to claim 3, wherein the purifying step comprises the steps of roasting the solidified substance containing lead carbonate to obtain lead oxide, reacting the lead oxide with a complexing solution to obtain a complex lead solution, introducing carbon dioxide into the complex lead solution to prepare high-purity lead carbonate, wherein the solidified substance containing lead carbonate in the step 2 is high-purity lead carbonate.
5. The method for preparing Plumbum Preparatium according to claim 4, wherein introducing carbon dioxide into the complex lead solution also produces a complex solution, and the complex solution is recycled for purifying the condensate containing lead carbonate.
6. The method of claim 4, wherein a dispersant is further added to the complexing solution.
7. The method for preparing red lead according to claim 4, wherein a dispersant is further added to the complex lead liquid before the complex lead liquid is introduced with carbon dioxide to prepare the high-purity lead carbonate.
8. The method of claim 1, wherein the exhaust gas from step 2 comprises carbon dioxide and sulfur dioxide.
9. The method for preparing the red lead according to claim 1, wherein in the step 1, the waste lead plaster is subjected to ammonia desulphurization, solid-liquid separation is carried out, and liquid of ammonium sulfate is obtained, the liquid of the ammonium sulfate reacts with calcium oxide or calcium hydroxide to generate lime and ammonia gas, and the ammonia gas is input into an ammonia water device.
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| PCT/CN2020/113343 WO2022047715A1 (en) | 2020-09-03 | 2020-09-03 | Method and apparatus for utilizing lead smelting tail gas treatment product |
| PCT/CN2020/113344 WO2022047716A1 (en) | 2020-09-03 | 2020-09-03 | Industrial tail gas treatment method and system therefor |
| CNPCT/CN2020/113344 | 2020-09-03 | ||
| CNPCT/CN2020/113343 | 2020-09-03 |
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| CN202011326999.0A Pending CN112661182A (en) | 2020-09-03 | 2020-11-24 | Preparation method of 4BS |
| CN202011327000.4A Pending CN112811464A (en) | 2020-09-03 | 2020-11-24 | Method and device for purifying condensate containing lead carbonate |
| CN202011326988.2A Pending CN112607767A (en) | 2020-09-03 | 2020-11-24 | Preparation method of red lead |
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| CN114709419A (en) * | 2022-02-28 | 2022-07-05 | 浙江铅锂智行科技有限公司 | Device and method for preparing anode lead paste additive |
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| CN112582606A (en) | 2021-03-30 |
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| WO2022048042A1 (en) | 2022-03-10 |
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