WO2022048042A1 - 一种铅酸蓄电池正极材料的制备方法 - Google Patents

一种铅酸蓄电池正极材料的制备方法 Download PDF

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WO2022048042A1
WO2022048042A1 PCT/CN2020/131215 CN2020131215W WO2022048042A1 WO 2022048042 A1 WO2022048042 A1 WO 2022048042A1 CN 2020131215 W CN2020131215 W CN 2020131215W WO 2022048042 A1 WO2022048042 A1 WO 2022048042A1
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lead
carbonate
oxide
acid battery
preparing
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PCT/CN2020/131215
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English (en)
French (fr)
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丁建华
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杭州铅锂智行科技有限公司
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Priority claimed from PCT/CN2020/113343 external-priority patent/WO2022047715A1/zh
Priority claimed from PCT/CN2020/113344 external-priority patent/WO2022047716A1/zh
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Publication of WO2022048042A1 publication Critical patent/WO2022048042A1/zh

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    • 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

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  • the invention relates to the field of lead-acid batteries.
  • the preparation method of the positive electrode material of lead-acid battery is to prepare refined lead by fire method, then cold-cut into balls, and prepare ⁇ -lead oxide powder by ball milling.
  • the preparation method needs to first smelt the waste lead paste containing lead sulfate to prepare crude lead. Since the melting point of lead sulfate is 1087°C, the smelting temperature needs to reach above 1100°C, and then the crude lead is prepared into refined lead, and then the oxidized lead is prepared in a ball mill.
  • Lead, ball mill power consumption is 300kwh/t lead oxide
  • lead oxide is added to the paste mixing machine, and additives, water, sulfuric acid, and red dan are added to the paste mixing machine together for paste mixing to realize the preparation of positive electrode materials.
  • the disadvantage of this method is that the waste lead paste needs to be smelted into crude lead at high temperature, the crude lead is refined into refined lead, the refined lead is cold-cut into balls and then ball-milled to prepare ⁇ -lead oxide lead powder, and then the paste is combined, and the temperature is raised during the process of combining the paste.
  • the present invention provides a method for preparing a positive electrode material for a lead-acid battery, which is characterized by comprising the following steps: Step 1: performing ammonia desulfurization on waste lead paste, and performing solid-liquid separation to obtain lead carbonate containing lead The solidified product; Step 2, the solidified product containing lead carbonate is smelted at high temperature to obtain alpha lead oxide, beta lead oxide, lead tetroxide and waste gas, and the waste gas is input into an ammonia water device to produce a desulfurizer comprising ammonia carbonate, The desulfurizer containing ammonia carbonate is used to desulfurize the waste lead paste in step 1; in step 3, the alpha lead oxide, beta lead oxide, and trilead tetroxide are combined with sulfuric acid.
  • the ⁇ -lead oxide is roasted at a temperature of 315-486 °C isolated from the air to generate ⁇ -lead oxide; then, the temperature is raised to 500-580 °C to roast the mixture of ⁇ -lead oxide and ⁇ -lead oxide; The mixture is calcined at 440-480 DEG C and bubbling air to obtain a mixture of red dan, beta lead oxide and alpha lead oxide.
  • the step 2 includes, smelting the solidified product at a high temperature to a first temperature to obtain ⁇ -lead oxide, taking out, and then smelting the solidified product containing lead carbonate at a high temperature to a second temperature, and passing oxygen to obtain.
  • step 2 the step of purifying the cured product containing lead carbonate is also included.
  • the step of purifying comprises, roasting the solidified product comprising lead carbonate to obtain lead oxide, reacting the lead oxide with the complex solution to obtain a complex lead solution, and passing the complex lead solution into the lead oxide.
  • Carbon dioxide is used to prepare high-purity lead carbonate, and the solidified product containing lead carbonate in the step 2 is high-purity lead carbonate.
  • carbon dioxide is introduced into the complexed lead solution to obtain a complexed solution, and the complexed solution is continuously circulated for purifying the solidified product containing lead carbonate.
  • a dispersant is also added to the complex solution.
  • a dispersant is also added to the complex lead liquid.
  • waste gas in the step 2 includes carbon dioxide and sulfur dioxide.
  • the waste lead paste is subjected to ammonia desulfurization, and the solid-liquid separation is carried out to obtain the liquid of ammonia sulfate, and the liquid of the ammonia sulfate reacts with calcium oxide or calcium hydroxide to generate lime and ammonia,
  • the ammonia gas is input to the ammonia water device.
  • the preparation method of the positive electrode material of the lead-acid battery of the present invention has the advantages of simple process and high efficiency.
  • FIG. 1 is a schematic diagram of a device for preparing a positive electrode material for a lead-acid battery of the present invention.
  • the lead-acid battery cathode material preparation device of the present invention comprises 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, Second solid-liquid separation device 7, purification device 6a, lead carbonate preparation device 6b, purification solid-liquid separation device 7a, lead carbonate solid-liquid separation device 7b.
  • the roasting device 1 includes a tail gas outlet 8, the tail gas outlet 8 is communicated with the air inlet 9 of the heat exchanger 2, the exhaust port 10 of the heat exchanger 2 is communicated with the air inlet 11 of the gas purification device 3 (3a), and the gas purification device 3 (3a)
  • the exhaust port 12 is communicated with the feed port 14 of the tail gas treatment product conversion device 4, the discharge port 15 of the tail gas treatment product conversion device 4 is communicated with the feed port 16 of the first solid-liquid separation device 5, and the first The discharge port 17 and the discharge port 18 of the solid-liquid separation device 5, the discharge port 17 is communicated with the feed port 19 of the gypsum generating device 6, the discharge port 18 is communicated with the feed port 20 of the roasting device 1, and the gypsum generating device
  • the exhaust port 25 of 6 is communicated with the air inlet 11 of the gas purification device 3, the discharge port 21 of the gypsum generating device 6 is communicated with the feed port 22 of the second solid-liquid separation device 7, and the second
  • the lead-acid battery cathode material preparation device of the present invention also includes a purification system for purifying the solidified product containing lead carbonate, and the solidified product containing lead carbonate separated from the first solid-liquid separation device 5 is transported to the roasting device 1, and solidified
  • the crude lead oxide obtained from the first roasting is transported to the purification device 6a through the feed port 27 of the purification device 6a, and the discharge port 28 of the purification device 6a is communicated with the feed port 29 of the purification solid-liquid separation device, and the purified solid-liquid separation liquid is
  • the discharge port 30 is connected with the feed port 31 of the high-purity lead carbonate preparation device 6b, the discharge port 32 of the high-purity lead carbonate preparation device 6b is connected with the feed port 33 of the lead carbonate solid-liquid separation device, and the high-purity lead carbonate solid-liquid separation
  • the mother liquor discharge port 34 of the device is communicated with the feed port 37 of the crude lead oxide purification device, the high-purity lead carbonate discharge
  • the preparation method of the positive electrode material of the lead-acid battery of the present invention is as follows: the liquid containing ammonium sulfate and ammonium carbonate in the gas purification device 3 flows into the tail gas treatment product conversion device 4 through a conveying pipeline, and the tail gas treatment product conversion device 4 is placed with lead sulfate containing lead sulfate.
  • the waste lead paste material, the liquid comprising ammonia sulfate and ammonium carbonate, that is, the desulfurizer flows into the tail gas treatment product conversion device 4 and reacts with lead sulfate to obtain a solid-liquid mixture comprising ammonia sulfate, lead carbonate and residual lead sulfate, and the solid-liquid mixture is obtained.
  • the separated liquid ammonium sulfate is sent to the gypsum generating device 6.
  • the gypsum generating device 6 contains a mixture of calcium oxide and water or calcium hydroxide. After ammonia is transported into the gypsum generating device 6, the reaction obtains calcium sulfate (common name gypsum) and ammonia water or ammonia water and ammonia gas, the obtained calcium sulfate and ammonia water are transported to the second solid-liquid separation device 7, and after the obtained calcium sulfate is washed, Sold as raw material.
  • the obtained ammonia gas is preferably also sent to the gas purification device 3 .
  • the solids containing lead carbonate and lead sulfate separated by the first solid-liquid separation device 5 are transported to the smelting device 1 and the roasting steps are as follows: 1) isolating the air at a temperature of 315-486 ° C and roasting for 1-5h to generate ⁇ -lead oxide; 2 ) post-heating to 500-580 °C and roasting for 5-30min to obtain the mixture of ⁇ lead oxide and ⁇ lead oxide in proportion (5%-25%); 3) then the mixture is calcined at 440-480 °C and air is blown for 1 -3h to get a mixture of red dan (5%-25%), beta lead oxide (5%-25%) and alpha lead oxide; 4) Combined paste; mix the above-mentioned lead powder mixture with conductive Fiber and positive battery additive
  • the solid containing lead carbonate and lead sulfate separated by the first solid-liquid separation device 5 of the present invention can also be transported to the smelting device 1 in batches for roasting, and a part of the solidified product is smelted at a high temperature to the first temperature to obtain ⁇ -lead oxide, Take out; then carry out high-temperature smelting to a second temperature on a part of the solidified product containing lead carbonate, pass oxygen to obtain lead tetroxide, namely red red, and take out; carry out high-temperature smelting on a part of the solidified product containing lead carbonate to a third temperature to obtain ⁇ Lead oxide, remove.
  • ⁇ -lead oxide, ⁇ -lead oxide and Hongdan are produced separately, so that the ratio between ⁇ -lead oxide, ⁇ -lead oxide and Hongdan can be better prepared.
  • the alpha lead oxide in the positive lead paste can quickly react with sulfuric acid to form lead sulfate during the curing process, and then the excess alpha lead oxide is combined with lead sulfate to form 3BS and a large number of 3BS network structures.
  • the combination of 3BS quickly generates a large amount of 4BS, which improves the bonding strength of the positive active material itself and the grid, and improves the cycle life and electrochemical performance of the battery.
  • Hongdan can speed up the forming speed and increase the initial discharge capacity of the battery.
  • the preparation of the positive electrode material of the present invention also includes the steps of purifying and refining the cured product containing lead carbonate.
  • the solidified product containing lead carbonate and lead sulfate separated by the first solid-liquid separation device 5 is transported to the smelting device 1 for roasting to obtain lead oxide, and the lead oxide may be alpha lead oxide.
  • the lead oxide enters the purification device 6a and reacts with the complex solution for purification.
  • the reaction is as follows: PbO+R+H2O ⁇ PbR 2+ +2OH - .
  • R is a food-grade dissolving and purifying complexing agent.
  • the complexing agents are: triethylamine, ethylenediamine, acetic acid, tartaric acid, oxalic acid, aspartic acid, alanine, sarcosine, phenylalanine, bright One or more of amino acid, histidine, asparagine, glycine, threonine, acetic acid, dispersing agent is polyvinylpyrrolidone, polyvinyl alcohol, sodium hydroxymethylcellulose, sodium dodecylbenzenesulfonate one or more of them.
  • the purified complex lead liquid is separated by the solid-liquid separation device 7a to obtain high-purity complex lead liquid and a small amount of solid lead slag, and the lead slag and desulfurization waste lead paste are continuously mixed together with desulfurization and roasting to prepare crude lead oxide, and the complex lead liquid enters.
  • High-purity lead carbonate preparation device 6b adding carbon dioxide to prepare high-purity lead carbonate, lead carbonate is separated by solid-liquid separation device 7b to obtain complex liquid and high-purity lead carbonate, the reaction is as follows: PbR 2+ +2OH - +CO2 ⁇ PbCO3 ⁇ + R+H2O, the complex liquid enters the purification device 6a and continues to circulate for the purification of crude lead oxide, and 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.
  • a dispersant such as polyvinylpyrrolidone
  • Lead oxide forms nano-scale particles.
  • the dispersant is added to the high-purity lead carbonate preparation device 6b and then carbon dioxide is passed through.
  • high-purity nano-scale lead carbonate can be prepared and fed into the roasting device 1 to prepare nano-alpha lead oxide, nano-beta lead oxide and nano-scale lead tetroxide.
  • the waste gas including carbon dioxide and sulfur dioxide gas obtained by roasting in the roasting device 1 is transported to the heat exchanger 2 through the pipeline for cooling treatment. Part of the waste gas after the cooling treatment is used for the preparation of high-purity lead carbonate, and the other part is transported to the storage tank through the pipeline.
  • the gas purification device 3 with ammonia water a liquid containing ammonia sulfate and ammonia carbonate is obtained, and the liquid of ammonia sulfate and ammonia carbonate is used for desulfurization and recycling of waste lead paste.
  • the method for preparing a positive electrode material for a lead-acid battery of the present invention involves smelting the desulfurized product of waste and old lead paste to directly obtain a composite material. On the one hand, the preparation efficiency of the positive electrode material is greatly improved; And the preparation of cathode materials to form an organic complete system.
  • the gas purification device 3 of the present invention is preferably an ammonia method gas purification device, including a first-stage ammonia water spray tower 3a, and may also include a second-stage spray tower 3b. If there is a small amount of incompletely absorbed gas in the first-stage ammonia water spray tower 3a It can overflow from the top of the first-level ammonia water spray tower 3a and be transported to the second-level spray tower 3b with ammonia water to absorb and prepare amine carbonate or ammonium bicarbonate solution.
  • the conversion device 4 ensures that the gas in the exhaust gas can be fully absorbed, so that as much gypsum as possible can be finally formed.
  • the solid-liquid separation device of the present invention can perform solid-liquid separation using a suitable method such as a scraper method and a centrifugal method.
  • the present invention may also include a washing device for washing the calcium sulfate solid precipitate for use.
  • hydrogen peroxide can be added to the ammonia gas purification device to convert sulfite ions into Sulfate ions form ammonium sulfate.
  • an oxygen blowing port can also be provided at the gypsum generating device 6, and the calcium sulfite that may be generated at the gypsum generating device 6 can be converted into calcium sulfate by blowing oxygen. It can also be set by adding hydrogen peroxide and blowing oxygen at the same time.
  • the present invention can also purify the cured product containing lead sulfate using the same purification method.
  • the method of the present invention can also only prepare red dan according to needs, as long as the corresponding temperature and the amount of air introduced can be controlled. That is, the solidified product containing lead carbonate is passed into air and smelted at a high temperature, and roasted at 440-480° C. with air blowing to obtain the red dan, and the red dan and waste gas are obtained, and the red dan is ready for use. The other way is the same.
  • the present invention prepares Hongdan through the desulfurized product of waste lead paste, and at the same time reuses the generated waste gas for preparing desulfurizer and gypsum, thereby forming a complete self-circulation system.
  • the method of the present invention can also only prepare lead oxide as required, as long as the corresponding temperature is controlled and the air is isolated. That is, the solidified product containing lead carbonate is calcined at 315-486 °C in isolation from the air to generate ⁇ -lead oxide; and then the mixture is heated to 500-580 °C to obtain a mixture of ⁇ -lead oxide and ⁇ -lead oxide.
  • lead oxide is prepared from the desulfurized product of waste lead paste, and the generated waste gas is reused for preparing desulfurizer and gypsum, thereby forming a complete self-circulation system.
  • the process from crude lead to refined lead is not required, which greatly reduces the production cost.
  • the method of the present invention can also further prepare 4BS with dilute sulfuric acid according to the prepared alpha lead oxide and beta lead oxide, the alpha lead oxide quickly reacts with sulfuric acid to generate lead sulfate, and then the excess alpha lead oxide is combined with lead sulfate to generate a large amount of 3BS 3BS network structure, and ⁇ -lead oxide quickly combined with part of 3BS after the formation of 3BS to quickly generate a large amount of 4BS.
  • 4BS improves the bonding strength of the positive active material itself and the grid, and improves the cycle life and electrochemical performance of the battery.
  • the sulfur removing agent of the present invention may also be a liquid containing only ammonium sulfate or ammonium carbonate or a mixed liquid thereof.

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  • Inorganic Chemistry (AREA)
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Abstract

本发明涉及一种铅酸蓄电池正极材料的制备方法，其特征在于，包括如下步骤：步骤1：对废旧铅膏进行氨法脱硫，并进行固液分离得到包含碳酸铅的固化物；步骤2，对包含碳酸铅的固化物进行高温熔炼，得到α氧化铅、β氧化铅、四氧化三铅和废气，所述废气输入氨水装置，生产包含碳酸氨的除硫剂，所述包含碳酸氨的除硫剂用于对步骤1中的废旧铅膏进行脱硫；步骤3，将所述α氧化铅、β氧化铅、四氧化三铅通过硫酸进行合膏。本发明的一种铅酸蓄电池正极材料的制备方法，工艺简单、效率高。

Description

一种铅酸蓄电池正极材料的制备方法 技术领域
本发明涉及铅酸蓄电池领域。
背景技术
目前铅酸蓄电池的正极材料制备方法，是先火法制备成精铅然后冷切制球并通过球磨制备成α-氧化铅粉，最后将该铅粉与电池添加剂混合加入水和稀硫酸和制成电池所需的正极活性物质铅膏。该制备方法需要先将含硫酸铅的废铅膏高温冶炼制备成粗铅，由于硫酸铅熔点1087℃，冶炼温度需要达到1100℃以上，之后再将粗铅制备成精铅，然后在球磨机制备氧化铅，球磨耗电300kwh/t氧化铅，最后将氧化铅加入合膏机，同时将添加剂、水、硫酸、红丹一起加入合膏机进行合膏，实现正极材料的制备。该方法缺点是需要将废铅膏高温冶炼制成粗铅，粗铅精炼成精铅，精铅冷切制球后球磨制备成α-氧化铅铅粉，再进行合膏，在合膏过程中升温生成β氧化铅同时加入红丹以及硫酸，整个过程能耗高，铅烟、铅尘、二氧化硫尾气污染严重，且工艺流程长，经济性差，合膏时还需要额外准备四氧化三铅即红丹，最后通过合膏制备成正极活性物质电化学性能不高等显著问题。
发明内容
为了解决上述技术问题，本发明提供了一种铅酸蓄电池正极 材料的制备方法，其特征在于，包括如下步骤：步骤1：对废旧铅膏进行氨法脱硫，并进行固液分离得到包含碳酸铅的固化物；步骤2，对包含碳酸铅的固化物进行高温熔炼，得到α氧化铅、β氧化铅、四氧化三铅和废气，所述废气输入氨水装置，生产包含碳酸氨的除硫剂，所述包含碳酸氨的除硫剂用于对步骤1中的废旧铅膏进行脱硫；步骤3，将所述α氧化铅、β氧化铅、四氧化三铅通过硫酸进行合膏。
进一步地，所述步骤2中，首先，在315-486℃温度隔绝空气焙烧生成α-氧化铅；然后，升温至500-580℃焙烧β氧化铅与α氧化铅的混合物；最后，降低温度将混合物在440-480℃并鼓入空气焙烧得到红丹、β氧化铅与α氧化铅的混合物。
进一步地，所述步骤2中包括，对固化物的进行高温熔炼到第一温度，得到α-氧化铅，取出，再对包含碳酸铅的固化物进行高温熔炼到第二温度，并通氧气得到四氧化三铅即红丹，取出；最后对包含碳酸铅的固化物进行高温熔炼到第三温度，得到β氧化铅，取出。
进一步地，所述步骤2之前还包括对所述包含碳酸铅的固化物进行提纯的步骤。
进一步地，所述提纯的步骤包括，将所述包含碳酸铅的固化物进行焙烧得到氧化铅，将所述氧化铅与络合液反应得到络合铅液，将所述络合铅液通入二氧化碳制备高纯碳酸铅，所述步骤2 中包含碳酸铅的固化物为高纯碳酸铅。
进一步地，所述络合铅液通入二氧化碳还制得络合液，络合液继续循环用于对包含碳酸铅的固化物进行提纯。
进一步地，所述络合液中还加入有分散剂。
进一步地，所述络合铅液通入二氧化碳制备高纯碳酸铅之前，所述络合铅液中还加入有分散剂。
进一步地，所述步骤2中的废气包括二氧化碳和二氧化硫。
进一步地，所述步骤1中，对废旧铅膏进行氨法脱硫，并进行固液分离还得到硫酸氨的液体，所述硫酸氨的液体与氧化钙或氢氧化钙反应生成石灰和氨气，所述氨气输入氨水装置。
本发明的一种铅酸蓄电池正极材料的制备方法，工艺简单、效率高。
附图说明
图1是本发明铅酸蓄电池正极材料制备装置的示意图。
具体实施方式
下面结合具体附图对本发明做进一步描述。
如图1所示，本发明铅酸蓄电池正极材料制备装置包括焙烧装置1、换热器2、气体净化装置3、尾气处理产物转化装置4、第一固液分离装置5、石膏生成装置6、第二固液分离装置7，提纯装置6a,碳酸铅制备装置6b,提纯固液分离装置7a,碳酸铅固 液分离装置7b。焙烧装置1包括尾气出口8，尾气出口8与换热器2的进气口9相通，换热器2的排气口10与气体净化装置3(3a)的进气口11连通，气体净化装置3(3a)排气口12与尾气处理产物转化装置4的进料口14连通，尾气处理产物转化装置4的出料口15与第一固液分离装置5的进料口16连通，第一固液分离装置5的出料口17和出料口18，出料口17与石膏生成装置6的进料口19连通，出料口18与焙烧装置1的进料口20连通，石膏生成装置6的排气口25与气体净化装置3的进气口11连通，石膏生成装置6的出料口21与第二固液分离装置7的进料口22连通，第二固液分离装置7的出料口23与气体净化装置3(3a)的进料口26连通，也可以与气体净化装置3(3a)的进气口11连通。本发明铅酸蓄电池正极材料制备装置还包括用于对包含碳酸铅的固化物进行提纯的提纯系统，从第一固液分离装置5分离出的包含碳酸铅的固化物输送到焙烧装置1，固化物第一次焙烧得到的粗品氧化铅通过提纯装置6a的进料口27输送到提纯装置6a，提纯装置6a的出料口28与提纯固液分离装置进料口29连通，提纯固液分离液体出料口30与高纯碳酸铅制备装置6b进料口31连通，高纯碳酸铅制备装置6b的出料口32与碳酸铅固液分离装置进料口33相连，高纯碳酸铅固液分离装置母液出料口34与粗氧化铅提纯装置进料口37连通，高纯碳酸铅出料口35与焙烧装置进料口36连通，焙烧装置1内焙烧高纯碳酸铅制备的氧化铅等固化物送入合膏装置并加入适当硫酸合膏 制备正极活性物质，焙烧产生的副产品二氧化碳可以经过热交换器2后与高纯碳酸铅制备装置进料口38连通循环再用于高纯碳酸铅的制备。
本发明铅酸蓄电池正极材料制备方法如下：将气体净化装置3内包含硫酸氨和碳酸氨的液体通过输送管道流动到尾气处理产物转化装置4内，尾气处理产物转化装置4内放置有含有硫酸铅的废旧铅膏物质，包含硫酸氨和碳酸氨的液体即除硫剂流动到尾气处理产物转化装置4内后与硫酸铅反应，得到包含硫酸氨、碳酸铅以及残余硫酸铅的固液混合物，固液混合物输送到第一固液分离装置5后，分离出的液体硫酸氨输送到石膏生成装置6内，石膏生成装置6内具有氧化钙和水的混合物或氢氧化钙，在分离出的液体硫酸氨输送到石膏生成装置6内后，反应得到硫酸钙(俗名石膏)和氨水或氨水和氨气，得到的硫酸钙和氨水输送到第二固液分离装置7，得到的硫酸钙进行洗涤后，作为原料卖出。为保证去除尾气中足够的二氧化碳或二氧化硫，以最终能生产尽可能多的石膏，得到的氨气最好也输送到气体净化装置3内。第一固液分离装置5分离出的包含碳酸铅和硫酸铅的固体输送到熔炼装置1内进行焙烧步骤如下：1)在315-486℃温度隔绝空气焙烧1-5h生成α-氧化铅；2)后生温至500-580℃焙烧5-30min得到占比(5％-25％)的β氧化铅与α氧化铅的混合物；3)然后将混合物料在440-480℃并鼓入空气焙烧1-3h得到红丹占比(5％-25％)，β氧化铅占比(5％-25％)与余量为α氧化铅的混 合物；4)合膏；将上叙铅粉混合物与导电纤维及正极电池添加剂按一定比例混合投入合膏装置进行干混5-10min,干混完毕快速加入10％-12％的纯水湿混5-10min,混合完毕在10-20min内加入密度为1.40g/ml的7％-9％合膏酸，加毕继续混合5-10min降温至45℃以下检测铅膏视比重合格出料涂板。合膏加酸过程中合膏温度不超过70℃，同时加酸过程合膏稳定在65-70℃之间稳定3-5min。通过控制焙烧温度和空气的量来得到相应的α-氧化铅、β氧化铅和红丹。本发明第一固液分离装置5分离出的包含碳酸铅和硫酸铅的固体也可以分批输送到熔炼装置1内进行焙烧，一部分固化物进行高温熔炼到第一温度，得到α-氧化铅，取出；再对包含碳酸铅的一部分固化物进行高温熔炼到第二温度，通氧气得到四氧化三铅即红丹，取出；对包含碳酸铅的一部分固化物进行高温熔炼到第三温度，得到β氧化铅，取出。从而单独生产α-氧化铅、β氧化铅和红丹，这样可以更好的调配α-氧化铅、β氧化铅和红丹之间的配比。
该正极铅膏中α氧化铅在固化过程中能快速与硫酸反应生成硫酸铅然后多余的α氧化铅再与硫酸铅结合生成3BS大量3BS网状结构、同时3BS生成后β氧化铅快速的与部分3BS结合快速生成大量4BS提高正极活性物质的自身及与板栅的结合强度提升电池的循环使用寿命及电化学性能。红丹在高强度极板化成过程中能加快化成速度并提升电池的初始放电容量。
本发明正极材料的制备，还包括对含有碳酸铅的固化物进行 提纯和细化的步骤。第一固液分离装置5分离出的包含碳酸铅和硫酸铅的固化物输送到熔炼装置1内焙烧得到氧化铅，氧化铅可以是α氧化铅。氧化铅进入提纯装置6a与络合液反应提纯，反应如下：PbO+R+H2O→PbR 2++2OH -。R为食品级溶解提纯络合剂，一般为络合剂为：三乙胺、乙二胺、乙酸、酒石酸、草酸、天冬氨酸、丙氨酸、肌氨酸、苯丙氨酸、亮氨酸、组氨酸、天冬酰胺、甘氨酸、苏氨酸、乙酸一种或多种，分散剂为聚乙烯吡咯烷酮，聚乙烯醇，羟甲基纤维素钠，十二烷基苯磺酸钠中一种或多种。提纯后的络合铅液通过固液分离装置7a分离得到高纯的络合铅液与少量固体铅渣，铅渣与脱硫废铅膏一起继续混合脱硫焙烧制备粗品氧化铅，络合铅液进入高纯碳酸铅制备装置6b,加入二氧化碳制备高纯碳酸铅，碳酸铅经过固液分离装置7b分离得到络合液与高纯碳酸铅，反应如下：PbR 2++2OH -+CO2→PbCO3↓+R+H2O，络合液进入提纯装置6a继续循环用于粗品氧化铅提纯，高纯碳酸铅进入焙烧装置1根据上述工艺步骤制备α氧化铅、β氧化铅和四氧化三铅。为达到更细的氧化铅，从而实现效果更好的正极材料的制备，可以在提纯装置6a、高纯碳酸铅制备装置6b中的至少一个中加入分散剂，如聚乙烯吡咯烷酮，分散剂可以使氧化铅形成纳米级颗粒，分散剂加入后在超声波的状态下进行反应会达到更好的效果，在高纯碳酸铅制备装置6b中加入分散剂后再通过二氧化碳。从而可以制得高纯纳米级碳酸铅进入焙烧装置1制备纳米α氧化铅、纳米β氧化铅和 纳米四氧化三铅。
焙烧装置1内焙烧得到的包括二氧化碳和二氧化硫的气体的废气通过管道输送到换热器2内进行降温处理，降温处理后的废气一部分用于高纯碳酸铅的制备，另一部分通过管道输送到存有氨水的气体净化装置3内，得到包含硫酸氨和碳酸氨的液体，硫酸氨和碳酸氨的液体用于废旧铅膏脱硫循环使用。
本发明铅酸蓄电池正极材料制备方法，将废旧铅膏脱硫后的产物，进行冶炼，直接得到合膏的材料，一方面正极材料的制备效率大大提高，另一方面将铅膏脱硫、冶炼尾气回收以及正极材料的制备形成一个有机完整的系统。
本发明的气体净化装置3最好为氨法气体净化装置，包括一级氨水喷淋塔3a，还可以包括二级喷淋塔3b，一级氨水喷淋塔3a如有少量未完全吸收的气体可以从一级氨水喷淋塔3a顶部溢出并通过管道输送至二级喷淋塔3b用氨水吸收制备碳酸胺或碳酸氢胺溶液，碳酸胺或碳酸氢胺溶度达到要求后输送至尾气处理产物转化装置4，这样确保尾气中的气体能够充分吸收，从而可以最终形成尽可能多的石膏。本发明的固液分离装置可以使用刮板法、离心法等合适的方式进行固液分离。本发明还可以包括洗涤装置，洗涤装置用于洗涤硫酸钙固体沉淀物以备用。为保证氨法气体净化装置能在吸收尾气后能得到尽可能多的硫酸氨，进而在后续能获得尽可能多的石膏，可以在氨法气体净化装置内加入 双氧水，将亚硫酸根离子转为硫酸根离子，形成硫酸氨。此外也可以在石膏生成装置6处，设置吹氧口，将石膏生成装置6处可能产生的亚硫酸钙，通过吹氧，转化成硫酸钙。也可以加入双氧水和吹氧同时进行设置。
此外，使用同样的提纯方法，本发明也可以对含有硫酸铅的固化物进行提纯。
本发明的方法也可以根据需要仅仅制备红丹，只要控制相应的温度和通入的空气量即可。也就是对包含碳酸铅的固化物通入空气并进行高温熔炼，在440-480℃并鼓入空气焙烧得到红丹，得到红丹和废气，红丹备用。其他方式相同。本发明通过废旧铅膏脱硫后的产物制备红丹，同时将产生的废气回用用于制备脱硫剂和石膏，形成了完整的自循环系统。
本发明的方法也可以根据需要仅仅制备氧化铅，只要控制相应的温度和隔绝空气即可。也就是对包含碳酸铅的固化物在315-486℃温度隔绝空气焙烧生成α-氧化铅；后升温至500-580℃焙烧得到的β氧化铅与α氧化铅的混合物。其他方式相同。本发明通过废旧铅膏脱硫后的产物制备氧化铅，同时将产生的废气回用用于制备脱硫剂和石膏，形成了完整的自循环系统。另外不需要粗铅到精铅的过程，大大降低生产成本。
本发明的方法也可以根据制备的α氧化铅和β氧化铅，再与稀硫酸一起进一步制备4BS，α氧化铅快速与硫酸反应生成硫酸 铅然后多余的α氧化铅再与硫酸铅结合生成3BS大量3BS网状结构、同时3BS生成后β氧化铅快速的与部分3BS结合快速生成大量4BS。4BS提高正极活性物质的自身及与板栅的结合强度提升电池的循环使用寿命及电化学性能。
本发明的除硫剂也可以是仅仅包含硫酸氨或碳酸氨的液体或其混合液体。
以上所述的实施例只是本发明的一种较佳的方案，并非对本发明作任何形式上的限制，在不超出权利要求所记载的技术方案的前提下还有其它的变体及改型。

Claims (10)

  1. 一种铅酸蓄电池正极材料的制备方法，其特征在于，包括如下步骤：步骤1：对废旧铅膏进行氨法脱硫，并进行固液分离得到包含碳酸铅的固化物；步骤2，对包含碳酸铅的固化物进行高温熔炼，得到α氧化铅、β氧化铅、四氧化三铅和废气，所述废气输入氨水装置，生产包含碳酸氨的除硫剂，所述包含碳酸氨的除硫剂用于对步骤1中的废旧铅膏进行脱硫；步骤3，将所述α氧化铅、β氧化铅、四氧化三铅通过硫酸进行合膏。
  2. 如权利要求1所述的一种铅酸蓄电池正极材料的制备方法，其特征在于，所述步骤2中，首先，在315-486℃温度隔绝空气焙烧生成α-氧化铅；然后，升温至500-580℃焙烧β氧化铅与α氧化铅的混合物；最后，降低温度将混合物在440-480℃并鼓入空气焙烧得到红丹、β氧化铅与α氧化铅的混合物。
  3. 如权利要求1所述的一种铅酸蓄电池正极材料的制备方法，其特征在于，所述步骤2中包括，对固化物的进行高温熔炼到第一温度，得到α-氧化铅，取出，再对包含碳酸铅的固化物进行高温熔炼到第二温度，并通氧气得到四氧化三铅即红丹，取出；最后对包含碳酸铅的固化物进行高温熔炼到第三温度，得到β氧化铅，取出。
  4. 如权利要求1-3任意一项所述的一种铅酸蓄电池正极材料的制备方法，其特征在于，所述步骤2之前还包括对所述包含碳酸铅的固化物进行提纯的步骤。
  5. 如权利要求4所述的一种铅酸蓄电池正极材料的制备方法，其特征在于，所述提纯的步骤包括，将所述包含碳酸铅的固化物进行焙烧得到氧化铅，将所述氧化铅与络合液反应得到络合铅液，将所述络合铅液通入二氧化碳制备高纯碳酸铅，所述步骤2中包含碳酸铅的固化物为高纯碳酸铅。
  6. 如权利要求5所述的一种铅酸蓄电池正极材料的制备方法，其特征在于，所述络合铅液通入二氧化碳还制得络合液，络合液继续循环用于对包含碳酸铅的固化物进行提纯。
  7. 如权利要求5所述的一种铅酸蓄电池正极材料的制备方法，其特征在于，所述络合液中还加入有分散剂。
  8. 如权利要求5所述的一种铅酸蓄电池正极材料的制备方法，其特征在于，所述络合铅液通入二氧化碳制备高纯碳酸铅之前，所述络合铅液中还加入有分散剂。
  9. 如权利要求1所述的一种铅酸蓄电池正极材料的制备方法，其特征在于，所述步骤2中的废气包括二氧化碳和二氧化硫。
  10. 如权利要求1所述的一种铅酸蓄电池正极材料的制备方法，其特征在于，所述步骤1中，对废旧铅膏进行氨法脱硫，并进行固液分离还得到硫酸氨的液体，所述硫酸氨的液体与氧化钙或氢氧化钙反应生成石灰和氨气，所述氨气输入氨水装置。
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