WO2022047715A1 - Method and apparatus for utilizing lead smelting tail gas treatment product - Google Patents

Method and apparatus for utilizing lead smelting tail gas treatment product Download PDF

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Publication number
WO2022047715A1
WO2022047715A1 PCT/CN2020/113343 CN2020113343W WO2022047715A1 WO 2022047715 A1 WO2022047715 A1 WO 2022047715A1 CN 2020113343 W CN2020113343 W CN 2020113343W WO 2022047715 A1 WO2022047715 A1 WO 2022047715A1
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Prior art keywords
ammonia
lead
tail gas
gas treatment
treatment product
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PCT/CN2020/113343
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French (fr)
Chinese (zh)
Inventor
周明明
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杭州铅锂智行科技有限公司
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Application filed by 杭州铅锂智行科技有限公司 filed Critical 杭州铅锂智行科技有限公司
Priority to PCT/CN2020/113343 priority Critical patent/WO2022047715A1/en
Priority to CN202011325470.7A priority patent/CN112582606B/en
Priority to CN202011325463.7A priority patent/CN112551573A/en
Priority to CN202011327000.4A priority patent/CN112811464A/en
Priority to CN202011326999.0A priority patent/CN112661182A/en
Priority to CN202011326988.2A priority patent/CN112607767A/en
Priority to PCT/CN2020/131215 priority patent/WO2022048042A1/en
Publication of WO2022047715A1 publication Critical patent/WO2022047715A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/48—Sulfur compounds
    • B01D53/50—Sulfur oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/64—Heavy metals or compounds thereof, e.g. mercury
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/77—Liquid phase processes
    • B01D53/78—Liquid phase processes with gas-liquid contact

Definitions

  • the invention relates to the technical field of lead smelting.
  • the invention of lead-acid batteries has a history of more than 100 years. At present, more than 80% of the batteries are still lead-acid batteries, and the lead resources for manufacturing lead-acid batteries are limited.
  • the state encourages the recycling and reuse of waste lead-acid batteries. Recycling. In the process of recycling and smelting lead-acid batteries, the disorderly discharge of lead dust and SO2, SO3 and nitrogen oxides is seriously polluted, especially the heavy metal lead is involved. Therefore, the state has very high environmental protection requirements for smelting pollution control: the existing In the technology, there are already methods for treating the tail gas produced by lead smelting, such as ammonia desulfurization, etc. Because the current tail gas treatment for lead smelting has not fully utilized the substances produced by the treatment, resulting in high tail gas treatment costs. question.
  • Step 1 smelting lead at a high temperature in a lead smelting device, and discharge the tail gas
  • Step 2 pass the discharged tail gas into a gas purification device to obtain ammonium carbonate and ammonium sulfate.
  • Step 3 the generated liquid comprising ammonium carbonate and ammonium sulfate is transported to the tail gas treatment product conversion device to obtain lead carbonate and lead sulfate solid precipitate and ammonium sulfate solution;
  • Step 4 the ammonia sulfate solution in step 3 is obtained It is transported to the gypsum generation device to obtain calcium sulfate and ammonia water, and the generated ammonia water is transported to the gas purification device, and the solid precipitates of lead carbonate and lead sulfate in step 3 are sent into the lead smelting device.
  • the step 3 also includes the step of solid-liquid separation of the solid precipitate of lead carbonate and lead sulfate and the ammonia sulfate solution
  • the step 4 also includes the step of solid-liquid separation of calcium sulfate and ammonia water.
  • step 4 the calcium sulfate in step 4 is washed for subsequent use.
  • step 4 ammonia gas is also generated, and the ammonia gas is sent to the gas purification device.
  • the gas purification device is an ammonia gas purification device.
  • the ammonia process gas purification device includes a first-level ammonia water spray tower and a second-level ammonia water spray tower, the tail gas discharged in the step 1 is passed into the first-level ammonia water spray tower, and the first-level ammonia water spray tower is A small amount of incompletely absorbed gas is transported from the primary ammonia water spray tower to the secondary spray tower to absorb and prepare a solution containing ammonia carbonate and ammonium sulfate. When the concentration of ammonia carbonate in the secondary spray tower reaches the requirement, it is transported to the tail gas treatment product conversion device.
  • the step 4 also includes the step of blowing oxygen into the gypsum generating device.
  • the invention also protects a device for utilizing the lead smelting tail gas treatment product.
  • the method and device for utilizing the lead smelting tail gas treatment product of the present invention reduce the cost of tail gas treatment and improve the efficiency of tail gas treatment.
  • Fig. 1 is the schematic diagram of the lead smelting tail gas treatment product utilization device of the present invention.
  • the lead smelting tail gas treatment product utilization device of the present invention comprises a smelting 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, and a gypsum generation device 6.
  • the gas port 11 is communicated, the exhaust port 12 of the gas purification device 3 (3a) is communicated with the feed port 14 of the tail gas treatment product conversion device 4, and the discharge port 15 of the tail gas treatment product conversion device 4 is connected with the first solid-liquid separation device 5.
  • the feed port 16 is connected, the discharge port 17 and the discharge port 18 of the first solid-liquid separation device 5, the discharge port 17 is communicated with the feed port 19 of the gypsum generating device 6, and the discharge port 18 is connected with the feed port of the smelting device 1.
  • the material port 20 is communicated, the exhaust port 25 of the gypsum generation device 6 is communicated with the air inlet 11 of the gas purification device 3, the discharge port 21 of the gypsum generation device 6 is communicated with the feed port 22 of the second solid-liquid separation device 7,
  • the discharge port 23 of the second solid-liquid separation device 7 is communicated with the feed port 26 of the gas purification device 3 (3a), and may also be communicated with the intake port 11 of the gas purification device 3 (3a).
  • the smelting apparatus 1 of the present invention is preferably a lead smelting apparatus.
  • the use cycle process of the lead smelting tail gas treatment product utilization device of the present invention is as follows: high temperature lead smelting is carried out in the lead smelting device 1, waste gas is formed in the smelting device 1 including carbon dioxide and sulfur dioxide, and the waste gas including the gas of carbon dioxide and sulfur dioxide can be transported through pipelines Carry out cooling treatment in the heat exchanger 2, and the waste gas after the cooling treatment can be transported to the gas purification device 3 containing ammonia water through pipelines to obtain a liquid containing ammonium sulfate and ammonium carbonate, and the liquid containing ammonium sulfate and ammonium carbonate is transported by The pipeline flows into the tail gas treatment product transformation device 4, the material containing lead sulfate in the tail gas treatment product transformation device 4, and the liquid containing ammonium sulfate and ammonium carbonate flows into the tail gas treatment product transformation device 4 and reacts with the
  • the solid-liquid mixture of ammonia, lead carbonate and residual lead sulfate after the solid-liquid mixture is sent to the first solid-liquid separation device 5, the separated liquid ammonia sulfate is sent to the gypsum generating device 6, and the gypsum generating device 6 has calcium oxide and calcium oxide.
  • the mixture of water or calcium hydroxide after the separated liquid ammonia sulfate 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, and the obtained calcium sulfate and ammonia water are transported to the second.
  • the obtained calcium sulfate is washed and sold as a 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 lead smelting device 1 to continue high-temperature lead smelting to obtain lead and waste gas.
  • the device of the invention processes the tail gas obtained from lead smelting through ammonia water to obtain a liquid containing ammonia sulfate and ammonia carbonate, and processes the liquid of ammonia sulfate and ammonia carbonate with the lead sulfate of waste lead paste to obtain ammonia sulfate.
  • the obtained ammonium sulfate is transported into the gypsum generating device 6, so that the ammonium sulfate obtained after the tail gas treatment and the lead sulfate reaction with the waste lead plaster are used together to obtain ammonium sulfate, which improves the output of ammonium sulfate and also improves the production of ammonium sulfate.
  • 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.
  • 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 produced at the gypsum generating device 6 is converted into calcium sulfate by blowing oxygen. It can also be set by adding hydrogen peroxide and blowing oxygen at the same time.
  • the transport of the products between the various components of the lead smelting tail gas treatment product utilization device of the present invention can be transported through pipelines through liquids and gases, and solids can be transported through conveyor belts, and can also be transported in other suitable ways.
  • other devices can be communicated through pipes.
  • the conveyor belt can be driven by a motor.
  • the circulation of liquid or gas in the pipeline can be realized by the pump or by the position setting of each device. For example, the position of the gas input device is higher than the position of the gas output device, and the position of the liquid input device is lower than the position of the gas output device.
  • the position of the gas purification device 3 is higher than the position of the heat exchanger 2
  • the position of the heat exchanger 2 is higher than the position of the smelting device 1
  • the position of the tail gas treatment product conversion device 4 is lower than the position of the gas purification device 3 to ensure that
  • the liquid containing ammonium sulfate and ammonium carbonate flows into the tail gas treatment product conversion device 4,
  • the position of the first solid-liquid separation device 5 is located below the tail gas treatment product conversion device 4
  • the position of the gypsum generation device 6 is located in the first solid-liquid separation device. 5 below the position and so on.
  • Such a setting can ensure that the entire lead smelting tail gas treatment product can be used to form a cycle.
  • the present invention conducts lead smelting for lead carbonate, the smelting temperature is determined by lead oxide, the melting point of lead oxide is 888°C, and the smelting temperature is above 900°C, while the melting point of lead sulfate is directly 1087°C for lead smelting with lead sulfate, and the smelting temperature needs to reach 1100°C As mentioned above, the present invention also achieves the effect of energy saving.
  • a method for utilizing a lead smelting tail gas treatment product of the present invention is as follows, step 1: carrying out high-temperature lead smelting in a lead smelting device, and mixing desulfurized lead paste (including solid lead carbonate and lead sulfate) with a certain proportion of pulverized coal, The iron powder is mixed and sent to the lead smelting device for high-temperature smelting to prepare crude lead, and the tail gas is discharged.
  • step 2 The tail gas from the smelting furnace is cooled by the heat exchanger and then enters the ammonia gas purification device for absorption, decarburization and desulfurization, and reacts to obtain a solution containing ammonia carbonate and ammonia sulfate.
  • Step 3 The solution containing ammonium carbonate and ammonium sulfate obtained by the ammonia method gas purification device is transported to the tail gas treatment product conversion device with built-in waste lead paste, and the solid precipitate containing lead carbonate and residual lead sulfate and ammonium sulfate solution are obtained.
  • the ammonia sulfate solution here includes the ammonia sulfate obtained by the reaction of ammonia carbonate and the lead sulfate in the lead paste, and may also include the ammonia sulfate obtained after desulfurization in step 2.
  • Step 4 the ammonia sulfate solution in step 3 is transported to the gypsum generating device, and put into quicklime or slaked lime for reaction to obtain gypsum, ammonia water, or ammonia water and ammonia gas, and the obtained gypsum and ammonia water are transported to the second solid-liquid separation device, The separated gypsum is rinsed with a small amount of pure water and used for later use. The obtained ammonia water and the ammonia gas are transported to the ammonia gas purification device through pipelines for absorbing and purifying the smelting tail gas.
  • the device is used for absorbing and purifying smelting tail gas; the solid precipitate of lead carbonate and residual lead sulfate in step 3 is sent to a lead smelting device for high-temperature smelting to prepare crude lead.
  • Step 3 may also include the step of transporting the solid precipitate of lead carbonate and residual lead sulfate and the ammonia sulfate solution into the first solid-liquid separation device for solid-liquid separation to obtain the solid precipitate of lead carbonate and residual lead sulfate and the ammonia sulfate solution.
  • the gas purification device is an ammonia gas purification device, including a first-level ammonia spray tower and a second-level ammonia spray tower, and a small amount of incompletely absorbed gas in the first-level ammonia spray tower is removed from the first-level ammonia spray tower.
  • the top overflows and is transported to the secondary spray tower to absorb and prepare a solution containing ammonia carbonate and ammonium sulfate.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Biomedical Technology (AREA)
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Abstract

A method for utilizing a lead smelting tail gas treatment product, comprising the following steps: step 1, performing high-temperature lead smelting in a lead melting apparatus (1), and discharging a tail gas; step 2, introducing the discharged tail gas into a gas purification apparatus (3) to obtain a liquid containing ammonium carbonate and ammonium sulfate; step 3, conveying the generated liquid containing ammonium carbonate and ammonium sulfate into a tail gas treatment product conversion apparatus (4) to obtain solid precipitates of lead carbonate and lead sulfate and an ammonium sulfate solution; and step 4, conveying the ammonium sulfate solution in step 3 to a gypsum generation apparatus (6) to obtain calcium sulfate and ammonia, conveying the generated ammonia to the gas purification apparatus (3), and feeding the solid precipitates of lead carbonate and lead sulfate in step 3 into the lead melting apparatus (1). Also disclosed is an apparatus for utilizing the lead smelting tail gas treatment product.

Description

一种铅冶炼尾气处理产物利用的方法及其装置A method and device for utilizing lead smelting tail gas treatment product 技术领域technical field
本发明涉及铅冶炼技术领域。The invention relates to the technical field of lead smelting.
背景技术Background technique
铅酸蓄电池的发明至今已有一百多年的历史，目前80％以上的蓄电池仍然是铅酸蓄电池，而制造铅酸蓄电池的铅资源是有限性的，国家鼓励对废旧铅酸蓄电池进行回收和循环利用。在铅酸蓄电池的回收冶炼过程中，产生的铅尘和SO2、SO3以及氮氧化合物无序排放污染严重，特别又涉及到重金属铅，所以国家对冶炼的污染治理环保要求非常高：现有的技术中，已存在对铅冶炼产生的尾气进行处理的方法，如氨法脱硫等，由于目前在针对铅冶炼的尾气处理的过程中，对处理产生的物质并没有充分利用，导致尾气处理成本高等问题。The invention of lead-acid batteries has a history of more than 100 years. At present, more than 80% of the batteries are still lead-acid batteries, and the lead resources for manufacturing lead-acid batteries are limited. The state encourages the recycling and reuse of waste lead-acid batteries. Recycling. In the process of recycling and smelting lead-acid batteries, the disorderly discharge of lead dust and SO2, SO3 and nitrogen oxides is seriously polluted, especially the heavy metal lead is involved. Therefore, the state has very high environmental protection requirements for smelting pollution control: the existing In the technology, there are already methods for treating the tail gas produced by lead smelting, such as ammonia desulfurization, etc. Because the current tail gas treatment for lead smelting has not fully utilized the substances produced by the treatment, resulting in high tail gas treatment costs. question.
发明内容SUMMARY OF THE INVENTION
为了解决上述技术问题，本发明提供了包括如下步骤：步骤1：在铅熔炼装置内高温铅冶炼，并排出尾气；步骤2，将排出的尾气通入气体净化装置，得到包含碳酸氨和硫酸氨 的液体；步骤3，将生成的包含碳酸氨和硫酸氨的液体输送到尾气处理产物转化装置，得到碳酸铅和硫酸铅固体沉淀物和硫酸氨溶液；步骤4：将步骤3中的硫酸氨溶液输送至石膏生成装置，得到硫酸钙、氨水，生成的氨水输送至气体净化装置，将步骤3中的碳酸铅和硫酸铅的固体沉淀物送入铅熔炼装置内。In order to solve the above-mentioned technical problems, the present invention provides the following steps: Step 1: smelting lead at a high temperature in a lead smelting device, and discharge the tail gas; Step 2, pass the discharged tail gas into a gas purification device to obtain ammonium carbonate and ammonium sulfate. Step 3, the generated liquid comprising ammonium carbonate and ammonium sulfate is transported to the tail gas treatment product conversion device to obtain lead carbonate and lead sulfate solid precipitate and ammonium sulfate solution; Step 4: the ammonia sulfate solution in step 3 is obtained It is transported to the gypsum generation device to obtain calcium sulfate and ammonia water, and the generated ammonia water is transported to the gas purification device, and the solid precipitates of lead carbonate and lead sulfate in step 3 are sent into the lead smelting device.
进一步地，所述步骤3还包括将碳酸铅和硫酸铅的固体沉淀物与硫酸氨溶液进行固液分离的步骤，所述步骤4还包括将硫酸钙、氨水进行固液分离的步骤。Further, the step 3 also includes the step of solid-liquid separation of the solid precipitate of lead carbonate and lead sulfate and the ammonia sulfate solution, and the step 4 also includes the step of solid-liquid separation of calcium sulfate and ammonia water.
进一步地，将步骤4中的硫酸钙洗涤备用。Further, the calcium sulfate in step 4 is washed for subsequent use.
进一步地，所述步骤4中还生成氨气，所述氨气输送至所述气体净化装置。Further, in the step 4, ammonia gas is also generated, and the ammonia gas is sent to the gas purification device.
进一步地，所述气体净化装置为氨法气体净化装置。Further, the gas purification device is an ammonia gas purification device.
进一步地，所述氨法气体净化装置包括一级氨水喷淋塔和二级氨水喷淋塔，所述步骤1中排出的尾气通入一级氨水喷淋塔，所述一级氨水喷淋塔少量未完全吸收的气体从一级氨水喷淋塔输送至二级喷淋塔吸收制备包含碳酸氨和硫酸氨的溶液，当二级喷淋塔内碳酸氨的浓度达到要求后输送至尾气处理产物转化装置。Further, the ammonia process gas purification device includes a first-level ammonia water spray tower and a second-level ammonia water spray tower, the tail gas discharged in the step 1 is passed into the first-level ammonia water spray tower, and the first-level ammonia water spray tower is A small amount of incompletely absorbed gas is transported from the primary ammonia water spray tower to the secondary spray tower to absorb and prepare a solution containing ammonia carbonate and ammonium sulfate. When the concentration of ammonia carbonate in the secondary spray tower reaches the requirement, it is transported to the tail gas treatment product conversion device.
进一步地，所述步骤4还包括向所述石膏生成装置内吹入氧气的步骤。Further, the step 4 also includes the step of blowing oxygen into the gypsum generating device.
本发明还保护了一种铅冶炼尾气处理产物利用的装置。The invention also protects a device for utilizing the lead smelting tail gas treatment product.
本发明的铅冶炼尾气处理产物利用的方法和装置，降低尾气处理成本、提高尾气处理效率。The method and device for utilizing the lead smelting tail gas treatment product of the present invention reduce the cost of tail gas treatment and improve the efficiency of tail gas treatment.
附图说明Description of drawings
图1是本发明铅冶炼尾气处理产物利用装置的示意图。Fig. 1 is the schematic diagram of the lead smelting tail gas treatment product utilization device of the present invention.
具体实施方式detailed description
下面结合具体附图对本发明做进一步描述。The present invention will be further described below with reference to the specific drawings.
如图1所示，本发明铅冶炼尾气处理产物利用装置包括熔炼装置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；熔炼装置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与熔炼装置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。As shown in Figure 1, the lead smelting tail gas treatment product utilization device of the present invention comprises a smelting 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, and a gypsum generation device 6. The second solid-liquid separation device 7; the smelting device 1 includes a tail gas outlet 8, the tail gas outlet 8 communicates with the air inlet 9 of the heat exchanger 2, and the exhaust port 10 of the heat exchanger 2 is connected to the inlet of the gas purification device 3 (3a). The gas port 11 is communicated, the exhaust port 12 of the gas purification device 3 (3a) is communicated with the feed port 14 of the tail gas treatment product conversion device 4, and the discharge port 15 of the tail gas treatment product conversion device 4 is connected with the first solid-liquid separation device 5. The feed port 16 is connected, the discharge port 17 and the discharge port 18 of the first solid-liquid separation device 5, the discharge port 17 is communicated with the feed port 19 of the gypsum generating device 6, and the discharge port 18 is connected with the feed port of the smelting device 1. The material port 20 is communicated, the exhaust port 25 of the gypsum generation device 6 is communicated with the air inlet 11 of the gas purification device 3, the discharge port 21 of the gypsum generation device 6 is communicated with the feed port 22 of the second solid-liquid separation device 7, The discharge port 23 of the second solid-liquid separation device 7 is communicated with the feed port 26 of the gas purification device 3 (3a), and may also be communicated with the intake port 11 of the gas purification device 3 (3a).
本发明的熔炼装置1最好为铅熔炼装置。本发明的铅冶炼尾气处理产物利用装置使用循环过程如下：铅熔炼装置1内进行高温铅冶炼，在熔炼装置1内形成废气包括二氧化碳和二氧化硫，将包括二氧化碳和二氧化硫的气体的废气可以通过管道输送到换热器2内进行降温处理，降温处理后的废气可以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，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内含有硫酸铅的物质，包含硫酸氨和碳酸氨的液体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铅熔炼装置1内继续进行高温铅冶炼，得到铅和废气。本发明的 装置通过对铅冶炼得到的尾气通过氨水进行处理得到产物包含硫酸氨和碳酸氨的液体进行一并处理，将硫酸氨和碳酸氨的液体与废旧铅膏的硫酸铅反应，得到硫酸氨，得到的硫酸氨输送到石膏生成装置6内，使得尾气处理后得到的硫酸氨和与废旧铅膏的硫酸铅反应得到硫酸氨一并进行利用，提高硫酸氨产量的同时也提高了硫酸氨的转化效率，并最终转化为石膏和氨水，从而保证产出最大量的石膏。由于石膏是原料，得到3份石膏只要消耗大概1份的生石灰，在石膏和生石灰市场价值相当的情况下，产生极高的经济价值。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。The smelting apparatus 1 of the present invention is preferably a lead smelting apparatus. The use cycle process of the lead smelting tail gas treatment product utilization device of the present invention is as follows: high temperature lead smelting is carried out in the lead smelting device 1, waste gas is formed in the smelting device 1 including carbon dioxide and sulfur dioxide, and the waste gas including the gas of carbon dioxide and sulfur dioxide can be transported through pipelines Carry out cooling treatment in the heat exchanger 2, and the waste gas after the cooling treatment can be transported to the gas purification device 3 containing ammonia water through pipelines to obtain a liquid containing ammonium sulfate and ammonium carbonate, and the liquid containing ammonium sulfate and ammonium carbonate is transported by The pipeline flows into the tail gas treatment product transformation device 4, the material containing lead sulfate in the tail gas treatment product transformation device 4, and the liquid containing ammonium sulfate and ammonium carbonate flows into the tail gas treatment product transformation device 4 and reacts with the lead sulfate to obtain a mixture containing sulfuric acid. The solid-liquid mixture of ammonia, lead carbonate and residual lead sulfate, after the solid-liquid mixture is sent to the first solid-liquid separation device 5, the separated liquid ammonia sulfate is sent to the gypsum generating device 6, and the gypsum generating device 6 has calcium oxide and calcium oxide. The mixture of water or calcium hydroxide, after the separated liquid ammonia sulfate 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, and the obtained calcium sulfate and ammonia water are transported to the second. In the solid-liquid separation device 7, the obtained calcium sulfate is washed and sold as a raw material. In order to ensure that enough carbon dioxide or sulfur dioxide in the exhaust gas is removed, so as to finally produce as much gypsum as possible, 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 lead smelting device 1 to continue high-temperature lead smelting to obtain lead and waste gas. The device of the invention processes the tail gas obtained from lead smelting through ammonia water to obtain a liquid containing ammonia sulfate and ammonia carbonate, and processes the liquid of ammonia sulfate and ammonia carbonate with the lead sulfate of waste lead paste to obtain ammonia sulfate. , the obtained ammonium sulfate is transported into the gypsum generating device 6, so that the ammonium sulfate obtained after the tail gas treatment and the lead sulfate reaction with the waste lead plaster are used together to obtain ammonium sulfate, which improves the output of ammonium sulfate and also improves the production of ammonium sulfate. conversion efficiency, and ultimately into gypsum and ammonia, thus ensuring the maximum output of gypsum. Since gypsum is the raw material, it takes only about 1 part of quicklime to obtain 3 parts of gypsum, which produces extremely high economic value when the market value of gypsum and quicklime are equal. 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. In order to ensure that the ammonia gas purification device can obtain as much ammonia sulfate as possible after absorbing the exhaust gas, and then obtain as much gypsum as possible in the follow-up, hydrogen peroxide can be added to the ammonia gas purification device to convert sulfite ions into Sulfate ions form ammonium sulfate. In addition, an oxygen blowing port can also be provided at the gypsum generating device 6, and the calcium sulfite that may be produced at the gypsum generating device 6 is converted into calcium sulfate by blowing oxygen. It can also be set by adding hydrogen peroxide and blowing oxygen at the same time.
本发明的铅冶炼尾气处理产物利用装置的各个组成部分之间产物的输送通过液体和气体可以通过管道传输、固体可以通过传输带传输，也可以通过其他合适的方式进行传输。铅熔炼装置1与第一固液分离装置5之间通过输送带连通之外，其他装置之间可以通过管道连通。输送带可以通过电机带动。管道内液体或气体的流通可以通过泵来实现，也可以通过各个装置的位置设置来实现，如气体输入装置的位置高于气体输出装置的位置，液体输入装置的位置低于气体输出装置的位置，也就是气体净化装置3的位置高于换热器2的位置，换热器2的位置高于熔炼装置1的位置，尾气处理产物转化装置4的位置低于气体净化装置3的位置，确保包含硫酸氨和碳酸氨的液体流动到尾气处理产物转化装置4内，第一固液分离装置5的位置位于尾气处理产物转化装置4的下方，石膏生成装置6的位置位于第一固液分离装置5的位置的下方等等。这样的设置可以确保整个铅冶炼尾气处理产物利用可以形成循环，原料只要不断提供废旧铅膏以及氢氧化钙或氧化钙和水，既可以实现得到石膏的循环***，该循环***在处理尾气的同时，对尾气处理产物进行利用，得到石膏的效率高、产量大。由于是循环***，反应完成后 的水不需要不断的外排，满足环保要求。同时本发明对碳酸铅进行铅冶炼，熔炼温度由氧化铅决定，氧化铅熔点888℃，熔炼温度在900℃以上，而直接用硫酸铅进行铅冶炼硫酸铅熔点1087℃，冶炼温度需要达到1100℃以上，本发明同时也实现节能效果。The transport of the products between the various components of the lead smelting tail gas treatment product utilization device of the present invention can be transported through pipelines through liquids and gases, and solids can be transported through conveyor belts, and can also be transported in other suitable ways. In addition to the communication between the lead smelting device 1 and the first solid-liquid separation device 5 through a conveyor belt, other devices can be communicated through pipes. The conveyor belt can be driven by a motor. The circulation of liquid or gas in the pipeline can be realized by the pump or by the position setting of each device. For example, the position of the gas input device is higher than the position of the gas output device, and the position of the liquid input device is lower than the position of the gas output device. , that is, the position of the gas purification device 3 is higher than the position of the heat exchanger 2, the position of the heat exchanger 2 is higher than the position of the smelting device 1, and the position of the tail gas treatment product conversion device 4 is lower than the position of the gas purification device 3 to ensure that The liquid containing ammonium sulfate and ammonium carbonate flows into the tail gas treatment product conversion device 4, the position of the first solid-liquid separation device 5 is located below the tail gas treatment product conversion device 4, and the position of the gypsum generation device 6 is located in the first solid-liquid separation device. 5 below the position and so on. Such a setting can ensure that the entire lead smelting tail gas treatment product can be used to form a cycle. As long as the raw materials are continuously supplied with waste lead plaster, calcium hydroxide or calcium oxide and water, a gypsum circulatory system can be realized. , Utilize the exhaust gas treatment product to obtain gypsum with high efficiency and large output. Because it is a circulatory system, the water after the reaction does not need to be discharged continuously, which meets the requirements of environmental protection. At the same time, the present invention conducts lead smelting for lead carbonate, the smelting temperature is determined by lead oxide, the melting point of lead oxide is 888°C, and the smelting temperature is above 900°C, while the melting point of lead sulfate is directly 1087°C for lead smelting with lead sulfate, and the smelting temperature needs to reach 1100°C As mentioned above, the present invention also achieves the effect of energy saving.
本发明的一种铅冶炼尾气处理产物利用的方法，如下，步骤1：在铅熔炼装置内进行高温铅冶炼，将脱硫铅膏(包含固态的碳酸铅和硫酸铅)与一定比例的煤粉，铁粉混合送入铅冶炼装置高温冶炼制备粗铅，并排出尾气。步骤2：冶炼炉出来的尾气经过换热器降温处理后进入氨法气体净化装置吸收进行脱碳，脱硫，反应得到包含碳酸氨和硫酸氨的溶液。步骤3：将氨法气体净化装置得到的包含碳酸氨和硫酸氨的的溶液输送至内置有废铅膏的尾气处理产物转化装置，得到含碳酸铅和残余硫酸铅的固体沉淀物与硫酸氨溶液，此处的硫酸氨溶液包括碳酸氨与铅膏中的硫酸铅反应得到的硫酸氨也可以包括步骤2中脱硫后得到的硫酸氨。步骤4：将步骤3中的硫酸氨溶液输送至石膏生成装置，并投入生石灰或熟石灰进行反应，得到石膏、氨水、或氨水和氨气，得到的石膏与氨水输送至第二固液分离装置，分离出的石膏用少量纯水淋洗后备用，得到的氨水和通过管道输送至氨法气体净化装置用于吸收净化冶炼尾气，反应过程溢出的氨气最好也通过管道输送至氨法气体净化装置用于吸收净化冶 炼尾气；将步骤3中的碳酸铅和残余硫酸铅的固体沉淀物送入铅冶炼装置高温冶炼制备粗铅。步骤3还可以包括将碳酸铅和残余硫酸铅的固体沉淀物与硫酸氨溶液输送入第一固液分离装置固液分离，得到碳酸铅和残余硫酸铅的固体沉淀物与硫酸氨溶液的步骤。A method for utilizing a lead smelting tail gas treatment product of the present invention is as follows, step 1: carrying out high-temperature lead smelting in a lead smelting device, and mixing desulfurized lead paste (including solid lead carbonate and lead sulfate) with a certain proportion of pulverized coal, The iron powder is mixed and sent to the lead smelting device for high-temperature smelting to prepare crude lead, and the tail gas is discharged. Step 2: The tail gas from the smelting furnace is cooled by the heat exchanger and then enters the ammonia gas purification device for absorption, decarburization and desulfurization, and reacts to obtain a solution containing ammonia carbonate and ammonia sulfate. Step 3: The solution containing ammonium carbonate and ammonium sulfate obtained by the ammonia method gas purification device is transported to the tail gas treatment product conversion device with built-in waste lead paste, and the solid precipitate containing lead carbonate and residual lead sulfate and ammonium sulfate solution are obtained. , the ammonia sulfate solution here includes the ammonia sulfate obtained by the reaction of ammonia carbonate and the lead sulfate in the lead paste, and may also include the ammonia sulfate obtained after desulfurization in step 2. Step 4: the ammonia sulfate solution in step 3 is transported to the gypsum generating device, and put into quicklime or slaked lime for reaction to obtain gypsum, ammonia water, or ammonia water and ammonia gas, and the obtained gypsum and ammonia water are transported to the second solid-liquid separation device, The separated gypsum is rinsed with a small amount of pure water and used for later use. The obtained ammonia water and the ammonia gas are transported to the ammonia gas purification device through pipelines for absorbing and purifying the smelting tail gas. The device is used for absorbing and purifying smelting tail gas; the solid precipitate of lead carbonate and residual lead sulfate in step 3 is sent to a lead smelting device for high-temperature smelting to prepare crude lead. Step 3 may also include the step of transporting the solid precipitate of lead carbonate and residual lead sulfate and the ammonia sulfate solution into the first solid-liquid separation device for solid-liquid separation to obtain the solid precipitate of lead carbonate and residual lead sulfate and the ammonia sulfate solution.
此外，步骤2中：气体净化装置为氨法气体净化装置，包括一级氨水喷淋塔和二级氨水喷淋塔，一级氨水喷淋塔少量未完全吸收的气体从一级氨水喷淋塔顶部溢出并通过管道输送至二级喷淋塔吸收制备包含碳酸氨和硫酸氨的溶液，当碳酸氨的浓度达到要求后输送至尾气处理产物转化装置进行利用。In addition, in step 2: the gas purification device is an ammonia gas purification device, including a first-level ammonia spray tower and a second-level ammonia spray tower, and a small amount of incompletely absorbed gas in the first-level ammonia spray tower is removed from the first-level ammonia spray tower. The top overflows and is transported to the secondary spray tower to absorb and prepare a solution containing ammonia carbonate and ammonium sulfate.
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。The above-mentioned embodiment is only a preferred solution of the present invention, and does not limit the present invention in any form, and there are other variations and modifications under the premise of not exceeding the technical solution recorded in the claims.

Claims (13)

  1. 一种铅冶炼尾气处理产物利用的方法，其特征在于，包括如下步骤：步骤1：在铅熔炼装置内高温铅冶炼，并排出尾气；步骤2，将排出的尾气通入气体净化装置，得到包含碳酸氨和硫酸氨的液体；步骤3，将生成的包含碳酸氨和硫酸氨的液体输送到尾气处理产物转化装置，得到碳酸铅和硫酸铅固体沉淀物和硫酸氨溶液；步骤4：将步骤3中的硫酸氨溶液输送至石膏生成装置，得到硫酸钙、氨水，生成的氨水输送至气体净化装置，将步骤3中的碳酸铅和硫酸铅的固体沉淀物送入铅熔炼装置内。A method for utilizing a lead smelting tail gas treatment product is characterized in that, comprising the following steps: step 1: smelting lead at high temperature in a lead smelting device, and discharging the tail gas; step 2, passing the discharged tail gas into a gas purification device to obtain a The liquid of ammonium carbonate and ammonium sulfate; Step 3, the generated liquid comprising ammonium carbonate and ammonium sulfate is transported to the tail gas treatment product conversion device to obtain lead carbonate and lead sulfate solid precipitate and ammonium sulfate solution; Step 4: step 3 The ammonia sulfate solution in the gypsum generation device is sent to the gypsum generating device to obtain calcium sulfate and ammonia water, and the generated ammonia water is sent to the gas purification device, and the solid precipitate of lead carbonate and lead sulfate in step 3 is sent into the lead smelting device.
  2. 如权利要求1所述的一种铅冶炼尾气处理产物利用的方法，其特征在于，所述步骤3还包括将碳酸铅和硫酸铅的固体沉淀物与硫酸氨溶液进行固液分离的步骤，所述步骤4还包括将硫酸钙、氨水进行固液分离的步骤。The method for utilizing a lead smelting tail gas treatment product according to claim 1, wherein the step 3 further comprises the step of solid-liquid separation of the solid precipitate of lead carbonate and lead sulfate and the ammonium sulfate solution, so that the The step 4 also includes the step of solid-liquid separation of calcium sulfate and ammonia water.
  3. 如权利要求2所述的一种铅冶炼尾气处理产物利用的方法，其特征在于，步骤4中还包括将硫酸钙洗涤备用的步骤。The method for utilizing a lead smelting tail gas treatment product according to claim 2, wherein step 4 further comprises a step of washing calcium sulfate for use.
  4. 如权利要求1、2或3任意一项所述的一种铅冶炼尾气处理产物利用的方法，其特征在于，所述步骤4中还生成氨气，所述氨气输送至所述气体净化装置。The method for utilizing a lead smelting tail gas treatment product according to any one of claims 1, 2 or 3, wherein ammonia gas is also generated in the step 4, and the ammonia gas is transported to the gas purification device .
  5. 如权利要求1、2或3任意一项所述的一种铅冶炼尾气处理产物利用的方法，其特征在于，所述气体净化装置为氨法气体净化装置。The method for utilizing a lead smelting tail gas treatment product according to any one of claims 1, 2 or 3, wherein the gas purification device is an ammonia gas purification device.
  6. 如权利要求5所述的一种铅冶炼尾气处理产物利用的方法，其特征在于，所述氨法气体净化装置包括一级氨水喷淋塔和二级氨水喷 淋塔，所述步骤1中排出的尾气通入一级氨水喷淋塔，所述一级氨水喷淋塔少量未完全吸收的气体从一级氨水喷淋塔输送至二级喷淋塔吸收制备包含碳酸氨和硫酸氨的溶液，当二级喷淋塔内碳酸氨的浓度达到要求后输送至尾气处理产物转化装置。The method for utilizing a lead smelting tail gas treatment product according to claim 5, wherein the ammonia process gas purification device comprises a primary ammonia water spray tower and a secondary ammonia water spray tower, and in the step 1, discharge The tail gas is passed into the first-level ammonia water spray tower, and a small amount of incompletely absorbed gas from the first-level ammonia water spray tower is transported from the first-level ammonia water spray tower to the second-level spray tower to absorb and prepare a solution comprising ammonia carbonate and ammonia sulfate, When the concentration of ammonia carbonate in the secondary spray tower reaches the requirement, it will be sent to the tail gas treatment product conversion device.
  7. 如权利要求1、2或3任意一项所述的一种铅冶炼尾气处理产物利用的方法，其特征在于，所述步骤4还包括向所述石膏生成装置内吹入氧气的步骤。The method for utilizing a lead smelting tail gas treatment product according to any one of claims 1, 2 or 3, wherein the step 4 further comprises the step of blowing oxygen into the gypsum generating device.
  8. 一种铅冶炼尾气处理产物利用的装置，包括铅冶炼装置、氨法气体净化装置、内置有废旧铅膏的尾气处理产物转化装置、内置有生石灰或熟石灰的石膏生成装置，其特征在于，所述铅冶炼装置与所述氨法气体净化装置连通，所述气体净化装置与所述尾气处理产物转化装置连通，所述所述尾气处理产物转化装置的产物包括硫酸铅和碳酸铅的固体沉淀物和硫酸氨溶液，所述铅冶炼装置用于接收所述硫酸铅和碳酸铅的固体沉淀物，所述石膏生成装置用于接收所述硫酸氨溶液，所述石膏生成装置的产物包括硫酸钙固体沉淀物和氨水溶液，所述氨法气体净化装置用于接收所述氨水溶液。A device for utilizing lead smelting tail gas treatment products, including a lead smelting device, an ammonia gas purification device, a tail gas treatment product conversion device with built-in waste lead plaster, and a gypsum generation device with built-in quicklime or slaked lime, characterized in that the The lead smelting device is communicated with the ammonia process gas purification device, the gas purification device is communicated with the tail gas treatment product conversion device, and the products of the tail gas treatment product conversion device include solid precipitates of lead sulfate and lead carbonate and Ammonia sulfate solution, the lead smelting device is used for receiving the solid precipitate of the lead sulfate and lead carbonate, the gypsum generating device is used for receiving the ammonia sulfate solution, and the product of the gypsum generating device includes calcium sulfate solid precipitation and ammonia solution, and the ammonia gas purification device is used for receiving the ammonia solution.
  9. 如权利要求8所述的一种铅冶炼尾气处理产物利用的装置，其特征在于，还包括第一固液分离装置和第二固液分离装置，所述第一固液分离装置用于固液分离所述尾气处理产物转化装置的产物，所述第二固液分离装置用于固液分离所述石膏生成装置的产物。The device for utilizing lead smelting tail gas treatment products according to claim 8, further comprising a first solid-liquid separation device and a second solid-liquid separation device, wherein the first solid-liquid separation device is used for solid-liquid separation The product of the tail gas treatment product conversion device is separated, and the second solid-liquid separation device is used for solid-liquid separation of the product of the gypsum generation device.
  10. 如权利要求8所述的一种铅冶炼尾气处理产物利用的装置， 其特征在于，还包括洗涤装置，所述洗涤装置用于洗涤所述硫酸钙固体沉淀物。The device for utilizing a lead smelting tail gas treatment product according to claim 8, further comprising a washing device, wherein the washing device is used for washing the calcium sulfate solid precipitate.
  11. 如权利要求8-10任意一项所述的一种铅冶炼尾气处理产物利用的装置，其特征在于，所述石膏生成装置的产物还包括氨气，所述氨法气体净化装置用于接收所述氨气。The device for utilizing a lead smelting tail gas treatment product according to any one of claims 8 to 10, wherein the product of the gypsum generating device further comprises ammonia gas, and the ammonia gas purification device is used to receive the Describe ammonia.
  12. 如权利要求8-10任意一项所述的一种铅冶炼尾气处理产物利用的装置，其特征在于，所述氨法气体净化装置包括一级氨水喷淋塔和二级氨水喷淋塔，所述铅冶炼装置与所述一级氨水喷淋塔连通，所述一级氨水喷淋塔与所述二级喷淋塔连通，所述一级氨水喷淋塔和所述二级氨水喷淋塔与所述尾气处理产物转化装置连通。The device for utilizing a lead smelting tail gas treatment product according to any one of claims 8-10, wherein the ammonia process gas purification device comprises a first-level ammonia spray tower and a second-level ammonia spray tower, so The lead smelting device is communicated with the first-level ammonia spray tower, the first-level ammonia spray tower is communicated with the second-level spray tower, and the first-level ammonia spray tower and the second-level ammonia spray tower are communicated with each other. communicated with the tail gas treatment product conversion device.
  13. 如权利要求8-10任意一项所述的一种铅冶炼尾气处理产物利用的装置，其特征在于，所述氨法气体净化装置内设置有双氧水。The device for utilizing the lead smelting tail gas treatment product according to any one of claims 8 to 10, wherein hydrogen peroxide is arranged in the ammonia gas purification device.
PCT/CN2020/113343 2020-09-03 2020-09-03 Method and apparatus for utilizing lead smelting tail gas treatment product WO2022047715A1 (en)

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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
CN202011325470.7A CN112582606B (en) 2020-09-03 2020-11-24 Preparation method and device of lead-acid storage battery positive electrode material
CN202011325463.7A CN112551573A (en) 2020-09-03 2020-11-24 Preparation method of lead oxide
CN202011327000.4A CN112811464A (en) 2020-09-03 2020-11-24 Method and device for purifying condensate containing lead carbonate
CN202011326999.0A CN112661182A (en) 2020-09-03 2020-11-24 Preparation method of 4BS
CN202011326988.2A CN112607767A (en) 2020-09-03 2020-11-24 Preparation method of red lead
PCT/CN2020/131215 WO2022048042A1 (en) 2020-09-03 2020-11-24 Method for preparing cathode material of lead-acid battery

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