CN110551900B - Combined treatment method for waste tin-plated copper scraps and copper electrolyte - Google Patents

Combined treatment method for waste tin-plated copper scraps and copper electrolyte Download PDF

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CN110551900B
CN110551900B CN201910933343.6A CN201910933343A CN110551900B CN 110551900 B CN110551900 B CN 110551900B CN 201910933343 A CN201910933343 A CN 201910933343A CN 110551900 B CN110551900 B CN 110551900B
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copper
tin
electrolyte
plated copper
waste
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CN110551900A (en
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肖驰名
肖之晔
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Hunan Renfa Material Technology Co ltd
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Hunan Renfa Material Technology Co ltd
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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
    • C22B15/00—Obtaining copper
    • C22B15/0063—Hydrometallurgy
    • C22B15/0084—Treating solutions
    • C22B15/0089—Treating solutions by chemical methods
    • C22B15/0091—Treating solutions by chemical methods by cementation
    • 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
    • C22B25/00—Obtaining tin
    • C22B25/04—Obtaining tin by wet 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
    • C22B25/00—Obtaining tin
    • C22B25/06—Obtaining tin from scrap, especially tin scrap
    • 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
    • C22B30/00—Obtaining antimony, arsenic or bismuth
    • C22B30/02—Obtaining antimony
    • 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
    • C22B30/00—Obtaining antimony, arsenic or bismuth
    • C22B30/04—Obtaining arsenic
    • 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
    • C22B30/00—Obtaining antimony, arsenic or bismuth
    • C22B30/06—Obtaining bismuth
    • 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
    • C22B7/006—Wet processes
    • 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

Abstract

The invention relates to a combined treatment method of waste crushed tin-plated copper and copper electrolyte, which comprises the steps of placing the waste crushed tin-plated copper without a covering on the surface in the copper electrolyte to be treated, leaching, and carrying out solid-liquid separation after the blue color of the copper electrolyte is faded to obtain leachate, the waste crushed copper after tin removal and replacement slag with the main component of sponge copper; blowing air or oxygen into the leaching solution to ensure that Sn is generated2+Is oxidized to Sn4+(ii) a Adjusting the pH value of the leaching solution to 4.5-5 to ensure that Sn is contained in the leaching solution4+And impurity elements are converted into precipitates, and then solid-liquid separation is carried out to obtain purified liquid and filter residues. The waste tin-plated copper crushed aggregates are taken from solid wastes such as urban mineral products or electronic garbage, can be directly used for purifying copper electrolyte without special pretreatment, and has obvious resource, environmental and economic benefits. The copper, tin, arsenic, antimony, bismuth, iron and other elements in the copper electrolyte can be removed together through the same process, and the process flow is simple and low in consumption.

Description

Combined treatment method for waste tin-plated copper scraps and copper electrolyte
Technical Field
The invention relates to a combined treatment method of waste tin-plated copper scraps and copper electrolyte, belonging to the field of hydrometallurgy and metal waste treatment.
Background
During the electrolytic refining of copper, the chemical dissolution of cuprous oxide in the anode and the dissolution of copper from anode mud cause the concentration of copper ions in the solution to gradually increase; although zinc, iron, tin, lead and nickel which are more electronegative than copper cannot be deposited on the cathode, the solution resistance is increased, and the power consumption is increased; impurity elements such as arsenic, antimony, bismuth and the like having a potential between copper and hydrogen are precipitated from the cathode when the concentration thereof is high to a certain level. In order to ensure that the electrolysis can be carried out smoothly and qualified cathode copper is electrolyzed, a certain amount of electrolyte must be extracted for purification in combination with the impurity limit concentration of the electrolyte.
At present, the purification processes or methods adopted at home and abroad are summarized into the following ones.
(1) The copper neutralization method or the direct concentration method is added to lead the concentration of copper sulfate in the electrolyte to reach a saturated state, and most of copper is generated in a form of crystal copper sulfate by cooling crystallization.
(2) The insoluble anode electrolytic deposition method is adopted to remove the copper in the electrolyte or the copper sulfate crystallization mother liquor, and simultaneously remove most of the impurities such as arsenic, antimony, bismuth and the like in the solution.
(3) And removing impurities such as copper, nickel, arsenic, antimony, tin, bismuth and the like in the electrolyte by adopting dialysis, extraction, ion exchange, coprecipitation and the like.
The methods have the defects of long process flow, high energy consumption, complex operation, environmental protection risk and the like. Such as: the copper-adding neutralization method needs to be carried out under the condition of oxygen blowing after the temperature is increased to 80-90 ℃; the insoluble anode electrolytic deposition method needs to adopt a tank voltage which is about 7 times higher than that of a tank voltage in electrolytic refining, has large power consumption and low current efficiency, and if the concentration of copper ions is improperly controlled, impurities and copper are discharged together, and the separation of highly toxic gas AsH is accompanied. Therefore, a process flow which is short in flow, low in consumption, safe and environment-friendly, and economic by the circulation of the waste impurity-removing clean liquid is necessary.
Modern industries such as electronics, communication, photoelectricity, audio-visual use tinned wire, tinned copper material and tinned copper spare in a large number, in the production and the use of tin-plated product, inevitably produce the useless crushed aggregates of a large amount of tinned copper, including useless tinned wire, electronic foot, hot tinning production can also produce hot tinned slag. The tin content of the waste crushed tin-plating materials is about 1-3%, the copper content is about 98%, and the tin content of the hot-dip tin-plating residues is about 30-90%, so that the hot-dip tin-plating residues have high recycling value. However, based on the physical and chemical properties of tin, copper and tin are difficult to separate in the extraction and metallurgy process.
At present, the waste tin-plated copper scraps are mainly recycled at home and abroad by a pyrogenic process, a pyrogenic process electrolysis method, an electrochemical method and a leaching and replacement method. However, the method has high energy consumption, high production cost and long process route, and can cause certain loss to copper due to the addition of other reagents, and the method has relatively isolated process and can not generate synergistic benefit.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a combined treatment method of the waste tin-plated copper scraps and the copper electrolyte, which integrates copper electrolyte purification and copper-tin separation of the waste tin-plated copper scraps, facilitates the copper-tin separation and the electrolyte purification, and further realizes the resource circulation and extraction metallurgy production with short process, less investment, simple equipment, economic circulation, green and low carbon.
In order to solve the technical problems, the technical scheme of the invention is as follows:
a combined treatment method of waste tin-plated copper scraps and copper electrolyte comprises the following steps:
placing the waste tin-plated copper crushed aggregates without the surface covering into a copper electrolyte to be treated, leaching, and after the blue color of the copper electrolyte is faded, carrying out solid-liquid separation to obtain a leaching solution, the waste tin-plated copper crushed aggregates and replacement slag mainly containing sponge copper;
blowing air or oxygen into the leaching solution to ensure that Sn is generated2+Is oxidized to Sn4+(ii) a Adjusting the pH value of the leaching solution to 4.5-5 to ensure that Sn is contained in the leaching solution4+And impurity elements are converted into precipitates, and then solid-liquid separation is carried out to obtain purified liquid and filter residues;
wherein the impurity element is one or more of As, Sb and Fe.
In the present invention, the waste crushed tin-plated copper material without surface covering is understood as exposed waste crushed tin-plated copper material with a surface wireless skin or other surface covering, and further, in the waste crushed tin-plated copper material, elemental tin is distributed on the surface layer of the waste crushed tin-plated copper material.
Optionally, the waste crushed tin-plated copper material comprises one or more of tin-plated copper wires, tin-plated copper materials and tin-plated copper pieces.
Generally, the grain size of the copper precipitate during leaching is extremely small, several orders of magnitude smaller than that of the tin-plated copper scrap or the tin-depleted copper scrap, and thus the copper precipitate and the tin-depleted copper scrap are easily separated.
Optionally, the waste tin-plated copper scraps are timely stirred during leaching, so that precipitates are prevented from being deposited on the surfaces of the waste tin-plated copper scraps and the leaching efficiency is prevented from being affected.
Optionally, the temperature of the copper electrolyte is controlled to be 50-60 ℃ during leaching.
Generally speaking, the reaction time is 25-45min in the leaching reaction process.
Generally, the addition amount of the tin-plated copper scrap can be obtained by theoretical calculation according to the copper content in the copper electrolyte, and is preferably 1 time or more, preferably 1.2 to 1.5 times of the theoretical calculation value.
Alternatively, the time for blowing air or oxygen is 45-75min, typically 50-70 min.
Optionally, the pH of the leachate is adjusted by adding lime.
Optionally, when the leachate is subjected to solid-liquid separation, the solid-liquid separation is realized through a plate-and-frame membrane filter press.
Optionally, the tin content in the tin-plated copper scrap is 1-3 wt%.
Optionally, in the copper electrolyte, the concentration of Cu is 30-55g/L, the concentration of As is 5-15g/L, the concentration of Sn is 0-10g/L, the concentration of Sb is 0-3g/L, and the concentration of Fe is 0.1-3.5 g/L.
Optionally, the waste copper scraps, the replacement slag and the filter residue can be cleaned respectively, and the used cleaning media, such as water, can be recycled mutually.
In the invention, the blue color of the copper electrolyte fades during leaching, which indicates that the copper ions in the copper electrolyte are completely or mostly removed; the replacement slag is generally mud-shaped, wherein the sponge copper has small granularity and high activity, mainly consists of Cu and O, and can be sent to a copper metallurgy system or used for preparing new electrolyte; the main component of the waste copper crushed aggregates after detinning is copper, and the waste copper crushed aggregates can be sent to a copper metallurgy system or used for preparing new electrolyte; the purified liquid has low impurity content, and can be returned to an electrolytic system for preparing new liquid; the filter residue is tin, arsenic, antimony, bismuth and iron slag which mainly contains tin element, contains a small amount of copper, lead and other components, and can be sent to a tin metallurgy system for comprehensive recovery of valuable elements.
The main reaction principle of the invention is as follows: in the leaching process, the metal tin in the tin-plated copper waste crushed aggregates is replaced in the copper electrolyteCu2+Generating Sn2+And copper sponge (very small particle size); in the neutralization precipitation step, air or oxygen is blown to make Sn2+Is oxidized to Sn4+In the presence of Fe2+Of (i) Fe2+Is oxidized into Fe3+Adjusting the pH value to 4.5-5 to obtain Sn in the solution4+Hydrolysis to form alpha-SnO2·H2O, which in turn is converted to beta- (SnO) having a stable structure2·H2O)5Colloidal, beta- (SnO)2·H2O)5The colloid traps ions or hydrolysis products formed by As, Sb, Fe and other elements in the solution to generate coprecipitation, and meanwhile, the addition of lime can improve the performance of the precipitate and facilitate liquid-solid separation and filtration.
Compared with the prior art, the invention has the following beneficial effects:
1) the waste tin-plated copper crushed aggregates are taken from solid wastes such as urban mineral products or electronic garbage, can be directly used for purifying copper electrolyte without special pretreatment, and has obvious resource, environmental and economic benefits.
2) The washing water of the process is circulated in a closed loop, the leached slag and the replacement slag filter residue are respectively returned to a copper metallurgy and tin smelting system, no waste water is discharged, no waste slag is generated, and impurity components are comprehensively recovered as valuable elements.
3) The copper, tin, arsenic, antimony, bismuth, iron and other elements in the copper electrolyte can be removed together through the same process, and the process flow is simple and low in consumption.
Drawings
FIG. 1 is a process flow diagram of the present invention.
Fig. 2 is a photograph of a real object of the tin-plated copper scrap of example 1.
FIG. 3 is a photograph of a physical example of the copper scrap after detinning in example 1.
FIG. 4 is a photograph of a copper sponge as a sample in example 1.
Detailed Description
The following description describes alternative embodiments of the invention to teach one of ordinary skill in the art how to make and use the invention.
Example 1
After copper electrolyte with chemical components of Cu48.70g/L, As10.1 g/L, Sn7.95g/L, Sb0.74g/L and Fe2.6g/L is purified by excessive tin-plated copper waste crushed aggregates through the process flow shown in figure 1, the purified copper electrolyte has the following contents of elements by detection: Cu0.32g/L, As0.41 g/L, Sn0.23g/L, Sb0.10g/L, Fe0.73g/L. The copper waste crushed aggregates after detinning have no residual tin, the tin content of the sponge copper is less than 0.3 percent, the purified slag contains 23.17wt percent of Sns, 2.26 wt percent of As2.26 wt percent and Fe0.4 wt percent, and the content of Sb and Cu in the purified slag is less than 0.2wt percent.
Example 2
Taking copper electrolyte with chemical components of Cu45.2 g/L, As7.8 g/L, Sn2.2 g/L, Sb1.27 g/L and Fe1.3 g/L, using excess tinning waste copper electronic feet, and purifying by the process flow shown in figure 1, wherein the purified liquid comprises the following elements: cu0.28 g/L, As0.45 g/L, Sn0.27 g/L, Sb0.33 g/L, Fe0.40g/L. The detinned waste copper electronic pin is detinned thoroughly, the tin content of the sponge copper is less than 0.3wt%, the purification slag contains 21.07wt% of Sns, 1.0 wt% of Ass and 0.24 wt% of Sbs, and the contents of Fe and Cu in the purification slag are less than 0.2 wt%.
Example 3
Taking chemical components of Cu38.17 g/L, Sb0.97 g/L, As9.12 g/L, Sn7.7 g/L and Fe1.12 g/L, and purifying with excessive tinned waste copper wires by the process flow shown in figure 1, wherein the purified liquid comprises the following elements: cu0.31 g/L, As0.37 g/L, Sn0.35 g/L, Sb0.27 g/L and Fe0.51g/L, the detinned waste copper wire has no apparent residual tin, the content of tin in the sponge copper is less than 0.3wt%, the content of Sn25.79 wt% in the purification slag, and the content of Sb, Cu, As and Fe in the purification slag is less than 0.3 wt%.
The foregoing examples are set forth to illustrate the present invention more clearly and are not to be construed as limiting the scope of the invention, which is defined in the appended claims to which the invention pertains, as modified in all equivalent forms, by those skilled in the art after reading the present invention.

Claims (8)

1. A combined treatment method of waste tin-plated copper scraps and copper electrolyte is characterized by comprising the following steps:
placing the waste tin-plated copper crushed aggregates without the surface covering into a copper electrolyte to be treated, leaching, and after the blue color of the copper electrolyte is faded, carrying out solid-liquid separation to obtain a leaching solution, the waste tin-plated copper crushed aggregates and replacement slag mainly containing sponge copper;
blowing air or oxygen into the leaching solution to ensure that Sn is generated2+Is oxidized to Sn4+(ii) a Adjusting pH of the leachate to 4.5-5, and adding Sn in the leachate4+Conversion to beta- (SnO)2·H2O)5Colloidal, beta- (SnO)2·H2O)5The colloid captures ions or hydrolysate formed by impurity elements in the solution to generate coprecipitation, so that Sn in the leaching solution is obtained4+And impurity elements are converted into precipitates, and then solid-liquid separation is carried out to obtain purified liquid and filter residues;
wherein the impurity element is one or more of As, Sb and Fe.
2. The combined treatment according to claim 1, wherein the temperature of the copper electrolyte during leaching is controlled to 50-60 ℃.
3. The combined treatment method according to claim 1, wherein the time for blowing air or oxygen is 45 to 75 min.
4. The integrated process of any one of claims 1 to 3, wherein the pH of the leach solution is adjusted by the addition of lime.
5. The integrated process according to any one of claims 1 to 3, wherein the solid-liquid separation of the leachate is carried out by a plate and frame membrane filter press.
6. The integrated processing method according to any one of claims 1 to 3, wherein the scrap tin-plated copper material includes one or more of tin-plated copper wire, tin-plated copper material, and tin-plated copper member.
7. The integrated processing method according to any one of claims 1 to 3, wherein the tin content in the tin-plated copper scrap is 1 to 3 wt%.
8. The combined treatment method according to any one of claims 1 to 3, wherein the copper electrolyte has a Cu concentration of 30 to 55g/L, an As concentration of 5 to 15g/L, an Sn concentration of 0 to 10g/L, an Sb concentration of 0 to 3g/L, and an Fe concentration of 0.1 to 3.5 g/L.
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CN111519213B (en) * 2020-05-09 2021-04-02 广东飞南资源利用股份有限公司 Electrolytic purification process for copper electrolyte

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3480477A (en) * 1967-05-19 1969-11-25 Metal Wire Recovery Corp Copper recovery
CA1117897A (en) * 1979-03-29 1982-02-09 George M. Freeman Continuous process for the purification of zinc plant electrolyte
US4351705A (en) * 1981-06-30 1982-09-28 Amax Inc. Refining copper-bearing material contaminated with nickel, antimony and/or tin
US5494649A (en) * 1991-10-03 1996-02-27 Cognis, Inc. Process for removing heavy metals from paint chips
JP4535786B2 (en) * 2004-06-18 2010-09-01 三井金属鉱業株式会社 Copper-containing tin powder, mixed powder containing the copper-containing tin powder, method for producing the copper-containing tin powder, and conductive paste using the copper-containing tin powder or the mixed powder
CN101643852B (en) * 2009-09-02 2011-10-12 北京科技大学 Heap-leaching method for separating copper and tin from tin-plated copper wires
CN102002594B (en) * 2010-12-17 2012-09-19 赖小洪 Method for recycling tin
CN102851514A (en) * 2012-10-08 2013-01-02 来宾华锡冶炼有限公司 Treatment method of coarse tin decoppered slag
CN102876903A (en) * 2012-10-08 2013-01-16 来宾华锡冶炼有限公司 Direct acidity oxygen pressure leaching treatment method of crude tin copper removal residues
CN104032362B (en) * 2013-06-27 2016-08-17 中石化上海工程有限公司 The processing method of waste solution of copper electrolysis
CN109825716A (en) * 2019-03-28 2019-05-31 湖南科技大学 A method of recycling copper and tin in waste and old tin plating copper-clad plate

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