CN113293303A - Method for producing lead alloy by synergistically reducing and smelting waste lead paste - Google Patents

Method for producing lead alloy by synergistically reducing and smelting waste lead paste Download PDF

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Publication number
CN113293303A
CN113293303A CN202110623530.1A CN202110623530A CN113293303A CN 113293303 A CN113293303 A CN 113293303A CN 202110623530 A CN202110623530 A CN 202110623530A CN 113293303 A CN113293303 A CN 113293303A
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China
Prior art keywords
waste
lead
smelting
producing
reducing
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CN202110623530.1A
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Chinese (zh)
Inventor
张忠堂
聂华平
严康
陈清
王瑞祥
刘志楼
李玉虎
徐志峰
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Jiangxi University of Science and Technology
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Jiangxi University of Science and Technology
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/001—Dry processes
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B5/00—General methods of reducing to metals
    • C22B5/02—Dry methods smelting of sulfides or formation of mattes
    • C22B5/10—Dry methods smelting of sulfides or formation of mattes by solid carbonaceous reducing agents
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/02—Making non-ferrous alloys by melting
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C11/00—Alloys based on lead
    • 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
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Environmental & Geological Engineering (AREA)
  • Processing Of Solid Wastes (AREA)
  • Manufacture And Refinement Of Metals (AREA)

Abstract

A method for producing lead alloy by synergistically reducing and smelting waste lead paste is characterized in that the waste lead paste is mixed with a waste circuit board, a reducing agent is added, and the reduction smelting is synergistically carried out to obtain reducing slag and lead alloy. The invention skillfully utilizes the iron-containing substances in the waste circuit boards to carry out sulfur fixation relative to the sulfur in the waste lead paste, the generated ferrous sulfide can also be used as an ironmaking raw material, and the reducing gas generated by the pyrolysis of the organic substances in the waste circuit boards is utilized, so that the aim of recycling solid waste resources is fulfilled, and the pollution in the reduction process is reduced.

Description

Method for producing lead alloy by synergistically reducing and smelting waste lead paste
Technical Field
The invention belongs to the field of recovery and treatment of waste minerals, and particularly relates to a method for producing lead alloy by synergistically reducing and smelting waste lead paste.
Background
With the increase of the demand of people for lead and the continuous shortage of single lead ore resources, the recovery of lead from secondary lead resources is a necessary way for the sustainable development of the lead smelting industry. As a main consumption field of lead, a large amount of waste lead-acid storage batteries are generated every year, and the waste lead-acid storage batteries become a main pollution source of the environment if not recycled. In the waste lead-acid storage battery, the waste electrolyte accounts for about 11-30%, the lead pole and the lead alloy grid account for 24-30%, the organic matter accounts for 22-30%, and the lead plaster accounts for 30-40%. The main component of the lead plaster is PbSO4、PbO2PbO, Pb and the like are important raw materials and main sources for producing secondary lead.
At present, the treatment process of the lead plaster mainly comprises a wet method and a fire method. The wet process for treating the lead plaster and recovering the metallic lead is always the main research direction of scholars at home and abroad. The common processes mainly comprise a waste polar plate solid-phase electrolysis method, a lead plaster leaching-electrodeposition method and a lead plaster reduction conversion desulfurization-leaching-electrodeposition method. Although the wet process for treating the lead plaster can effectively prevent and treat lead pollution and has good environmental benefit, the wet process has the advantages of multiple equipment links, large investment and immature technology and does not have industrial popularization conditions. The pyrogenic process has the advantages of simple flow, less equipment investment, high processing capacity, large-scale production and the like. The direct reduction method for treating the lead plaster is the most common pyrogenic process in the industry at present, but the temperature in the reduction process is higher and can reach over 1250 ℃, the energy consumption is higher, and meanwhile, the volatilization loss of main metal Pb and compounds thereof in the reduction smelting process is larger and the direct yield of the metal is lower due to the high reduction temperature.
Disclosure of Invention
The technical problem to be solved by the invention is to overcome the defects and shortcomings mentioned in the background technology, and to provide a method for producing lead alloy by using a conversion desulfurization-low temperature reduction smelting method and co-reduction smelting waste lead paste, wherein the method can partially eliminate lead and SO2Pollution and increase of vertical shrinkageRate, reduced energy consumption, etc.
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
a method for producing lead alloy by synergistically reducing and smelting waste lead paste is characterized in that the waste lead paste is mixed with a waste circuit board, a reducing agent is added, and the reduction smelting is synergistically carried out to obtain reducing slag and lead alloy.
The iron-containing phase in the waste circuit board can decompose lead-containing compounds (sulfate and higher oxide) in the waste lead plaster at a lower temperature to convert the lead-containing compounds into corresponding oxides (lead oxide), and the lead alloy is generated by the reaction of reducing gas (such as phenol and the like) generated by the pyrolysis of organic matters in the waste circuit board and the addition of a reducing agent; the sulfur is mainly fixed in the reducing slag in the form of ferrous sulfide in the reducing process, the pollution to the environment is reduced, other valuable metals such as Cu, Sn, Ni and the like in the waste circuit board and lead form low-melting-point alloy in the reducing process and are enriched in a metal phase, the ferrous sulfide generated in the reducing process can also be used as an iron-making raw material, the recycling of solid and waste resources is realized, and the main chemical reactions in the reducing process are as follows:
PbSO4+Fe+C→Pb+FeS+CO2(g)，
PbO+C→Pb+CO2(g)。
preferably, in the method for producing the lead alloy by synergistically reducing and smelting the waste lead paste, the reduction temperature is 600-900 ℃ in the reduction smelting process, and the reduction smelting time is 60-180 min.
Preferably, the mass ratio of the waste lead plaster to the waste circuit board is (1-1.6): (0.8-1.2).
In the method for producing the lead alloy by synergistically reducing and smelting the waste lead paste, preferably, the reducing agent is a carbonaceous reducing agent with carbon content of not less than 85%.
In the method for producing the lead alloy by synergistically reducing and smelting the waste lead paste, preferably, the addition amount of the reducing agent accounts for 3-9% of the total mass of the waste lead paste and the waste circuit board. The organic matter in the waste circuit board is pyrolyzed to generate reducing gas, so that the addition amount of the carbonaceous reducing agent can be reduced, and the metal reduction efficiency and the reasonable reducing agent consumption in the reduction process are improved.
Preferably, the main components of the waste circuit board comprise 10-30% of Cu, 5-15% of Fe, 1-3% of Sn, 1-3% of Ni, 3-7% of Al and SiO27-10% of organic matter.
In the method for producing lead alloy by co-reduction smelting of waste lead paste, preferably, the main component of the waste lead paste comprises PbSO4 60-63％、PbO2 18-22％、PbO 3-6％、Pb 0.4-0.8％。
Compared with the prior art, the invention has the advantages that:
(1) the invention skillfully utilizes the iron-containing substances in the waste circuit boards to carry out sulfur fixation relative to the sulfur in the waste lead paste, the generated ferrous sulfide can also be used as an ironmaking raw material, and the reducing gas generated by the pyrolysis of the organic substances in the waste circuit boards is utilized, so that the aim of recycling solid waste resources is fulfilled, and the pollution in the reduction process is reduced.
(2) The method for producing the lead alloy by reducing and smelting the waste lead paste has the advantages of simple operation process, little pollution, easy control and suitability for industrial application, and the yield of the alloy can reach more than 92 percent.
Detailed Description
In order to facilitate an understanding of the present invention, the present invention will be described more fully and in detail with reference to the preferred embodiments, but the scope of the present invention is not limited to the specific embodiments below.
Unless otherwise defined, all terms of art used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention.
Unless otherwise specifically stated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be prepared by existing methods.
The chemical composition of the waste lead paste treated in the following examples includes (%): PbSO4 60.5、PbO220.6, PbO 5.3 and Pb0.5, wherein the chemical composition of the waste circuit board comprises (%): cu 23, Fe 13.2, Sn 2.4, Ni 2.6, Al 3.3, SiO2 7.4。
Example 1:
the invention relates to a method for producing lead alloy by synergistically reducing and smelting waste lead paste, which comprises the following operation steps:
(1) 100g of waste lead paste subjected to cracking, separation and pressure filtration, 80g of waste circuit board and 5.4g of reducing agent coke (the content of C is 85%) are weighed, mixed uniformly and then put into a corundum crucible.
(2) And (3) putting the crucible into an electric furnace for reduction smelting, introducing argon as protective gas in the reduction smelting process, controlling the reduction temperature to be 700 ℃, reducing for 90min, and taking out a reduction product after the reduction is finished.
(3) The reducing slag and the lead alloy were separated, weighed, and analyzed, yielding 81.78g of lead alloy (Pb 69.5, Cu 24.9%, Sn 2.62%, Ni 2.81%) and 65g of reducing slag (Pb 12.78%, Fe 17.41%, S9.33%). The alloy yield in the reduction process is 94%, and the sulfur fixation rate can reach 95%.
Example 2:
the invention relates to a method for producing lead alloy by synergistically reducing and smelting waste lead paste, which comprises the following operation steps:
(1) 100g of waste lead paste subjected to cracking, separation and pressure filtration, 120g of waste circuit board and 11g of reducing agent coke (C content 85%) are weighed, mixed uniformly and then put into a corundum crucible.
(2) And (3) putting the crucible into an electric furnace for reduction smelting, introducing argon as a protective gas in the process, controlling the reduction temperature to be 800 ℃, reducing for 120min, and taking out a reduction product after the reduction is finished.
(3) The reducing slag and the lead alloy were separated, weighed, and analyzed, to obtain 94.3g of lead alloy (Pb 54.1, Cu 37.3%, Sn 3.9%, Ni 4.2%) and 89g of reducing slag (Pb 15.27%, Fe 17.8%, S7.12%). The alloy yield in the reduction process is 96 percent, and the sulfur fixation rate can reach 99 percent.

Claims (7)

1. A method for producing lead alloy by synergistically reducing and smelting waste lead paste is characterized in that the waste lead paste is mixed with a waste circuit board, a reducing agent is added, and the reduction smelting is synergistically carried out to obtain reducing slag and lead alloy.
2. The method for producing lead alloy by co-reduction smelting of waste lead paste as claimed in claim 1, wherein the reduction temperature in the reduction smelting process is 600 ℃ to 900 ℃, and the time for reduction smelting is 60min to 180 min.
3. The method for producing a lead alloy by co-reductive smelting of waste lead paste as claimed in claim 1, wherein the mass ratio of the waste lead paste to the waste circuit board is (1-1.6): (0.8-1.2).
4. The method for producing a lead alloy by co-reductive smelting of waste lead paste as claimed in claim 1, wherein said reducing agent is a carbonaceous reducing agent having a carbon content of not less than 85%.
5. The method for producing lead alloy by co-reductive smelting of waste lead paste as claimed in claim 4, wherein the amount of the reducing agent added is 3-9% of the total mass of the waste lead paste and the waste circuit board.
6. The method for producing a lead alloy by co-reductive melting of waste lead paste according to any one of claims 1 to 5, wherein the waste circuit boards mainly comprise Cu 10-30%, Fe 5-15%, Sn 1-3%, Ni 1-3%, Al 3-7%, SiO 3%2 7-10％。
7. The method for producing a lead alloy by co-reductive smelting of waste lead paste according to any one of claims 1 to 5, wherein the main component of the waste lead paste comprises PbSO4 60-63％、PbO2 18-22％、PbO 3-6％、Pb 0.4-0.8％。
CN202110623530.1A 2021-06-04 2021-06-04 Method for producing lead alloy by synergistically reducing and smelting waste lead paste Pending CN113293303A (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3111396A1 (en) * 1980-03-24 1982-04-29 Sony Corp., Tokyo GUIDING PASTE
CN101335370A (en) * 2008-07-11 2008-12-31 东莞市松山科技集团有限公司 Process implement full cycle regeneration of lead acid battery
US8323595B1 (en) * 2011-09-03 2012-12-04 Toxco, Inc. Recovery of high purity lead oxide from lead acid battery paste
CN103667712A (en) * 2013-12-12 2014-03-26 中南大学 Method for smelting lead-containing waste and copper-containing waste synchronously in molten pool
CN112030002A (en) * 2020-09-10 2020-12-04 江西理工大学 Method for producing blister copper by directly oxygen-enriched smelting from waste circuit boards

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3111396A1 (en) * 1980-03-24 1982-04-29 Sony Corp., Tokyo GUIDING PASTE
CN101335370A (en) * 2008-07-11 2008-12-31 东莞市松山科技集团有限公司 Process implement full cycle regeneration of lead acid battery
US8323595B1 (en) * 2011-09-03 2012-12-04 Toxco, Inc. Recovery of high purity lead oxide from lead acid battery paste
CN103667712A (en) * 2013-12-12 2014-03-26 中南大学 Method for smelting lead-containing waste and copper-containing waste synchronously in molten pool
CN112030002A (en) * 2020-09-10 2020-12-04 江西理工大学 Method for producing blister copper by directly oxygen-enriched smelting from waste circuit boards

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
ZHONGTANG ZHANG等: "thermodynamic analysis of the bottom-blown direct reduction of lead sulfate with carbon", 《JOURNAL OF THERMAL ANALYSIS AND CALORIMETRY》 *
朱光明等: "《资源化视角的污染控制理论与实践》", 31 December 2019, 上海交通大学出版社 *
邹伟钊等: "废铅酸蓄电池铅膏铵法预脱硫过程的动力学分析", 《环境工程学报》 *

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