CN110484736B - Method for purifying zinc sulfate leaching solution to remove copper - Google Patents
Method for purifying zinc sulfate leaching solution to remove copper Download PDFInfo
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- CN110484736B CN110484736B CN201910932712.XA CN201910932712A CN110484736B CN 110484736 B CN110484736 B CN 110484736B CN 201910932712 A CN201910932712 A CN 201910932712A CN 110484736 B CN110484736 B CN 110484736B
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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
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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
- C22B19/00—Obtaining zinc or zinc oxide
- C22B19/20—Obtaining zinc otherwise than by distilling
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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
- C22B19/00—Obtaining zinc or zinc oxide
- C22B19/32—Refining zinc
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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
- C22B7/006—Wet processes
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- 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
A method for purifying and removing copper from zinc sulfate leaching solution is characterized in that waste tin-plated copper crushed material is added into the zinc sulfate leaching solution, and after the reaction is finished, solid-liquid separation is carried out to obtain leaching residue, leaching solution and replacement residue; 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 (4) converting the copper-containing solution into a precipitate, and then carrying out solid-liquid separation to obtain a copper-removed solution and tin-containing filter residues. The waste crushed tin-plated copper material is obtained from city mineral products or electronic garbage and is used directly in zinc sulfate leaching liquid to eliminate copper, antimony, iron and arsenic, and the product is spongy copper, and may be used directly in copper electrolytic compounding liquid or copper pyrometallurgy with obvious resource, environment and economic benefit.
Description
Technical Field
The invention relates to a method for purifying and removing copper from zinc sulfate leaching solution, in particular to a method for purifying and removing copper from zinc sulfate leaching solution and recycling waste tin-plated copper scraps in non-ferrous metal hydrometallurgy.
Background
In non-ferrous metal extraction metallurgy, zinc calcine or other zinc-containing materials (such As smoke dust containing zinc oxide) are subjected to middle leaching to generate neutral leachate, the leachate contains many impurities, such As Cu, As, Fe, Sb, Cd, Co, Ni and the like, the impurities have great harm to the production of zinc sulfate or the zinc electrolytic deposition process, all harmful impurities are removed through solution purification, and the produced qualified purified solution can be sent to a zinc electrolytic tank or used for producing zinc sulfate chemical products.
At present, the method for purifying zinc sulfate solution at home and abroad to remove copper, iron, arsenic and antimony impurities in the zinc sulfate solution generally adopts the following flow:
firstly, in the leaching process, controlling the end-point acidity to lead Fe3+Completely hydrolyzing the precipitate, and removing arsenic, antimony and partial impurities;
② firstly adding hydrogen peroxide (H) into the extract2O2) Of Fe2+Complete oxidation to Fe3+Then adjusting the pH value with lime slurry to Fe3+The precipitate is completely hydrolyzed and precipitated,simultaneously removing arsenic, antimony and partial impurities;
thirdly, after removing arsenic, iron, antimony and partial impurities, replacing and removing copper in the zinc sulfate solution by zinc powder.
However, in the first method (i), Fe may be present2+Conversion to Fe3+Incomplete, so that the iron removal effect is not ideal; secondly, the iron, arsenic, antimony and copper removal are carried out step by step, the process flow is long, and the process is uneconomical; and thirdly, the zinc powder is adopted to remove copper, and the simple substance zinc product is converted into an intermediate product of zinc, so that the cost and the benefit are to be rationalized. Therefore, it is necessary to establish a short-flow, low-cost, resource-recycling type purification method.
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 wt%, the copper content is about 98wt%, and the tin content of the hot-dip tin-plating residues is about 30-90 wt%, 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
The invention aims to provide a method for separating copper and tin from waste tin-plated copper scraps, integrating the purification and copper removal of zinc sulfate leachate and the separation of copper and tin from the waste tin-plated copper scraps, promoting the separation of the copper and the tin and simultaneously realizing the purification and copper removal of the zinc sulfate leachate based on the problems in the prior art, so as to further realize a resource circulation and extraction metallurgy production mode with short process, less investment, simple equipment, economic circulation, environmental protection and low carbon.
A method for purifying and removing copper from zinc sulfate leaching solution comprises the following steps:
s1, adding the waste crushed tin-plated copper into the zinc sulfate leaching solution, and after the reaction is finished, carrying out solid-liquid separation to obtain leaching slag, leaching solution and replacement slag;
wherein, the surface of the waste tin-plated copper scraps is not covered with a covering; the leaching slag mainly comprises tin-removed copper waste crushed aggregates, and the replacement slag mainly comprises sponge copper;
s2, blowing air or oxygen into the leachate obtained in S1 to ensure that Sn2+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 (4) converting the copper-containing solution into a precipitate, and then carrying out solid-liquid separation to obtain a copper-removed solution and tin-containing filter residues.
Further, in S1, the zinc sulfate leaching solution is injected into a purification leaching tank, then the waste crushed tin-plated copper is added in batches, and after the reaction is finished, solid-liquid separation is carried out to obtain leaching slag, leaching solution and replacement slag. Generally, the leaching reaction time is 35-40 min.
In S1, the zinc sulfate leaching solution contains Zn50-500g/L and Cu0.5-5g/L, Fe0-5g/L, As0-5g/L, Sb0-5 g/L.
In S1, the tin content in the waste tin-plated copper scraps is 1-3 wt%. The addition amount of the waste tin-plated copper scraps can be determined according to Cu in the zinc sulfate solution2+The contents, the total amount of the zinc sulfate solution and the tin content in the waste tin-plated copper scraps are obtained by comprehensive calculation.
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.
Further, the waste crushed material of tinned copper comprises one or more of tinned copper wires, tinned copper materials, tinned copper pieces and hot tinned slag, and the tinned copper pieces comprise tinned copper electronic pins.
In general, during leaching, the particle size of copper precipitates is extremely small and is several orders of magnitude smaller than that of the tin-plated copper scrap or the tin-removed copper scrap, and therefore, the copper precipitates and the tin-removed copper scrap are easily separated, and therefore, in the solid-liquid separation at S1, two solid phases of the leaching slag and the substitution slag are easily separated.
In S1, the temperature of the zinc sulfate leaching solution is controlled to be 50-60 ℃.
In S1, the zinc sulfate leach solution is a zinc sulfate leach stock solution, or a solution obtained by dilution.
In S1, when the blue color of the zinc sulfate leaching solution fades, the reaction is finished; or taking zinc sulfate leaching solution and standing, and detecting Cu in supernate2+When concentration of Cu2+When the concentration of (D) is lower than a preset value, the reaction is finished.
Further, the preset value is 0.01-0.05 g/L, and can be determined according to the purification requirement of the zinc sulfate leaching solution.
In S2, the time for blowing air is 55-65 min.
In S2, the pH of the leachate is adjusted by adding lime. Preferably, the slaked lime is added directly.
In S2, the solid-liquid separation of the leachate is carried out by a plate-and-frame membrane filter press.
And S2, washing the tin-containing filter residue to obtain purified residue.
Furthermore, the leached residues and the filter residues are directly washed by using water as a cleaning medium, the washing water can be mutually recycled, and the insufficient part can be added with additional water.
In the invention, the replacement slag is mainly newly generated sponge copper, 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, and the sponge copper is integrally in a mud shape and is easy to separate from the tin-removed copper waste crushed aggregates with relatively large size; the leached slag is mainly tin-removed copper waste crushed material and can be returned to a copper smelting system for copper recovery treatment; the impurity content of the liquid after copper removal is low, and the liquid can be sent to the next operation flow; the filter residue and the purification slag are tin, arsenic, antimony and iron slag which mainly contain tin elements, and can be sent to a tin metallurgy system for carrying out comprehensive recovery of valuable elements.
The main reaction principle of the invention is as follows: in the leaching process, the metallic tin in the tin-plated copper waste crushed aggregates replaces the Cu in the zinc sulfate leaching solution2+Generating Sn2+And copper sponge (very small particle size); neutralization and precipitation stepBlowing air 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 advantages:
1) the waste tin-plated copper crushed aggregates are taken from solid wastes such as urban mineral products or electronic garbage and the like, are directly used for purifying zinc sulfate leaching solution to remove copper, antimony, iron and arsenic, one of the obtained products (filter residues) is sponge copper, can be directly used for copper electrolysis solution preparation or pyrometallurgy of copper, and has obvious resource, environmental and economic benefits.
2) The washing water is circulated in a closed loop in the process, the filter residue is respectively returned to copper metallurgy and tin smelting systems, no waste water is discharged, no waste residue is generated, and impurity components are comprehensively recovered as valuable elements.
3) The same process flow completes the purification and the copper removal of the zinc sulfate leaching solution and the purification and the removal of the impurities such as arsenic, iron, antimony and the like, and has simple process flow and low consumption.
Drawings
FIG. 1 is a process flow diagram of the present invention.
FIG. 2 is a photograph of a leached residue 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 zinc sulfate leachate with chemical components of Zn150.70g/L, Cu0.95g/L, Fe0.15g/L, As0.25g/L and Sb0.71g/L is purified by excessive tin-plated copper waste crushed aggregates through the process flow shown in the figure 1, copper-removing zinc sulfate leachate (Cu0.32g/L, As0.05 g/L, Sb0.03g/L and Fe0.04g/L) is obtained. The appearance of the tin-removed copper waste crushed aggregates is free of residual tin, the tin content of the sponge copper is less than 0.3 percent, the purified slag contains 18.72 percent of Sns, 1.57 percent of Ass and 1.4 percent of Fes, and the Cu content in the purified slag is lower than 0.2 percent;
wherein, each percentage represents the mass percentage content.
Example 2
Zinc sulfate leachate with chemical components of Zn140.57g/L, Cu1.17g/L, As1.8g/L, Sb1.27g/L and Fe1.3g/L is taken, and is purified by using excessive tin-plating waste copper electronic feet through the process flow shown in figure 1 to obtain copper-removing zinc sulfate leachate (Cu0.08 g/L, As0.07g/L, Sb0.03g/L and Fe0.01g/L). The detinned waste copper electronic pin has thorough detinning, the tin content of the sponge copper is less than 0.3 percent, the purified slag contains 13.77 percent of Sns, 1.0 percent of As1.83 percent of Sb0.83 percent, and the Cu content of the purified slag is less than 0.2 percent;
wherein, each percentage represents the mass percentage content.
Example 3
Taking zinc sulfate leachate with chemical components of Zn137.07g/L, Cu1.03g/L, Sb0.97g/L, As1.12g/L and Fe1.12 g/L, purifying the zinc sulfate leachate with excessive tinning waste copper wires by the process flow shown in the figure 1 to obtain copper-removing zinc sulfate leachate (Cu0.11g/L, As0.009 g/L, Sb0.27g/L and Fe0.51g/L), wherein the tin-removing waste copper wires have no apparent residual tin, the tin content of sponge copper is less than 0.3%, the purification slag contains 17.78% of Sn0.98%, 0.57% of Sb0.57% and Fe1.7%, and the Cu content of the purification slag is lower than 0.3%;
wherein, each percentage represents the mass percentage content.
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 method for purifying and removing copper from zinc sulfate leaching solution is characterized by comprising the following steps:
s1, adding the waste crushed tin-plated copper into the zinc sulfate leaching solution, and after the reaction is finished, carrying out solid-liquid separation to obtain leaching slag, leaching solution and replacement slag;
wherein, the surface of the waste tin-plated copper scraps is not covered with a covering; the leaching slag mainly comprises tin-removed copper waste crushed aggregates, and the replacement slag mainly comprises sponge copper; the zinc sulfate leaching solution contains Zn50-500g/L and Cu0.5-5g/L, Fe0-5g/L, As0-5g/L, Sb0-5 g/L;
s2, blowing air or oxygen into the leachate obtained in S1 to ensure that Sn2+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+Conversion to alpha-SnO2·H2O, which in turn is converted to beta- (SnO) having a stable structure2·H2O)5Colloidal, beta- (SnO)2·H2O)5And (3) trapping ions or hydrolysis products formed by As, Sb and Fe elements in the solution by using the colloid, generating coprecipitation, and then carrying out solid-liquid separation to obtain copper-removed liquid and tin-containing filter residue.
2. The method as claimed in claim 1, wherein in S1, the tin content in the scrap tin-plated copper is 1-3 wt%.
3. The method according to claim 1, wherein in S1, the temperature of the zinc sulfate leach solution is controlled to be 50-60 ℃.
4. The method according to claim 1, wherein in S1, the blue fading of zinc sulfate leachate indicates the completion of the reaction; or taking zinc sulfate leaching solution and standing, and detecting Cu in supernate2+When concentration of Cu2+When the concentration of (D) is lower than a preset value, the reaction is finished.
5. The method according to claim 1, wherein the time for blowing the air is 55-65min in S2.
6. The process according to any one of claims 1 to 5, wherein in S2, the pH of the leachate is adjusted by adding lime.
7. The method according to any one of claims 1 to 5, wherein in S2, the solid-liquid separation of the leachate is carried out by a plate-and-frame membrane filter press.
8. The method according to any one of claims 1 to 5, wherein after S2, the tin-containing filter residue is washed to obtain a purified residue.
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| CN110241308A (en) * | 2019-04-08 | 2019-09-17 | 无锡市安盛再生资源有限公司 | The recovery method and system of tin metal in a kind of nitric acid type tin-stripping wastewater |
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| US7416680B2 (en) * | 2001-10-12 | 2008-08-26 | International Business Machines Corporation | Self-cleaning colloidal slurry composition and process for finishing a surface of a substrate |
| CN100359026C (en) * | 2003-03-14 | 2008-01-02 | 中国有色工程设计研究总院 | Method and apparatus for removing copper, cadmium and cobalt from zinc sulfate solution |
| CN102002594B (en) * | 2010-12-17 | 2012-09-19 | 赖小洪 | Method for recycling tin |
| EE201000096A (en) * | 2010-12-31 | 2012-08-15 | Tartu Ülikool | Method and Preparation of Nanocolloidal SnO2 Water Salts |
| CN102409180B (en) * | 2011-11-02 | 2013-07-17 | 郴州丰越环保科技股份有限公司 | Metallurgical process for recovering metal copper, lead, zinc and tin from copper refining waste slag |
| CN102676820A (en) * | 2012-06-08 | 2012-09-19 | 大兴安岭云冶矿业开发有限公司 | Treatment method of zinc sulfate leach solution |
| CN103014355B (en) * | 2012-12-13 | 2014-12-24 | 马永涛 | Multi-metal comprehensive recycling process for copper smelting ash |
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| CN110241308A (en) * | 2019-04-08 | 2019-09-17 | 无锡市安盛再生资源有限公司 | The recovery method and system of tin metal in a kind of nitric acid type tin-stripping wastewater |
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