CN102676820A - Treatment method of zinc sulfate leach solution - Google Patents
Treatment method of zinc sulfate leach solution Download PDFInfo
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- CN102676820A CN102676820A CN2012101887140A CN201210188714A CN102676820A CN 102676820 A CN102676820 A CN 102676820A CN 2012101887140 A CN2012101887140 A CN 2012101887140A CN 201210188714 A CN201210188714 A CN 201210188714A CN 102676820 A CN102676820 A CN 102676820A
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- zinc sulfate
- leach liquor
- sulfate leach
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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
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- 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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Abstract
The invention discloses a treatment method of a zinc sulfate leach solution, which comprises the following steps: A) adding zinc into a zinc sulfate leach solution to carry out replacement reaction, and carrying out solid-liquid separation on the zinc sulfate leach solution to obtain copper concentrate and a medium supernatant; and B) removing iron from the medium supernatant, and purifying to obtain purified residues. The treatment method of a zinc sulfate leach solution can greatly enhance the recovery rate of copper in the zinc sulfate leach solution, and greatly enhance the grade of the recycled copper concentrate.
Description
Technical field
The present invention relates to field of metallurgy, in particular to a kind of treatment process of zinc sulfate leach liquor.
Background technology
In conventional process zinc sulfide concentrates technical matters flow process; Generally adopt the zinc sulfate leach liquor is sent to cleaning section through behind the iron removal step, obtain to purify slag after the removal of impurities, handle to reclaim method of metal copper purifying slag again; The copper recovery of this method is lower, has caused the waste of resource.
Summary of the invention
The present invention is intended to solve at least one of technical problem that exists in the prior art.
The contriver is finding through further investigation back, and in the treating processes of existing zinc sulfate leach liquor, because the neutralizing hydrolysis deironing generally carries out under pH is the condition of 5.0-5.2, about 70% cupric ion can hydrolytic precipitation gets in the slag and is removed under this pH.Cause the recovery of copper to be merely about 20% like this, caused the waste of resource.
For this reason, one object of the present invention is to propose the treatment process that a kind of copper reclaims higher zinc sulfate leach liquor.
For realizing above-mentioned purpose; A kind of treatment process of zinc sulfate leach liquor is proposed according to embodiments of the invention; The treatment process of said zinc sulfate leach liquor may further comprise the steps: A) zinc is joined in the zinc sulfate leach liquor to carry out replacement(metathesis)reaction, then said zinc sulfate leach liquor is carried out solid-liquid separation to obtain copper ore concentrates and middle supernatant; And B) supernatant in said is carried out deironing and purifies to be purified slag.
According to the treatment process of the zinc sulfate leach liquor of the embodiment of the invention through removing copper in the said zinc sulfate leach liquor earlier, removing iron in the said zinc sulfate leach liquor again; Thereby not only can reclaim the most copper in the said zinc sulfate leach liquor; The recovery of copper can be reached more than 85%, and can improve the grade (bringing up to 90%) that reclaims the copper ore concentrates that obtains widely by 35%.
In addition, the treatment process of zinc sulfate leach liquor according to the above embodiment of the present invention can also have following additional technical characterictic:
According to one embodiment of present invention, said steps A) comprising: A-1) said zinc sulfate leach liquor is filtered; A-2) zinc is joined in the filtering said zinc sulfate leach liquor of process to carry out said replacement(metathesis)reaction; And A-3) said zinc sulfate leach liquor is carried out solid-liquid separation to obtain said copper ore concentrates and said middle supernatant.Through before carrying out said replacement(metathesis)reaction, said zinc sulfate leach liquor being filtered, thereby can the solid impurity in the said zinc sulfate leach liquor be removed, can avoid said solid impurity to be entrained in the said copper ore concentrates like this, influence the grade of said copper ore concentrates.
According to one embodiment of present invention, said steps A) in, the acid content of said zinc sulfate leach liquor smaller or equal to 5g/L and copper content more than or equal to 1000mg/L.Can avoid influencing the copper in the said zinc sulfate leach liquor of zinc dust precipitation like this because of the acid content of said zinc sulfate leach liquor is too high.
According to one embodiment of present invention, said steps A) in, said replacement(metathesis)reaction is carried out under the condition of 45 degree-85 degree.Can improve the speed of response of said replacement(metathesis)reaction so widely.
According to one embodiment of present invention, said steps A) in, the reaction times of said replacement(metathesis)reaction is 20 minutes-40 minutes.Said replacement(metathesis)reaction is carried out fully, so that the most copper in the said zinc sulfate leach liquor is cemented out.
According to one embodiment of present invention, said steps A) in, the speed with 65 rev/mins-84 rev/mins when carrying out said replacement(metathesis)reaction stirs said zinc sulfate leach liquor.Zinc powder and said zinc sulfate leach liquor are mixed fully, thereby can improve the speed of response of said replacement(metathesis)reaction widely.
According to one embodiment of present invention, the copper content of said middle supernatant is that 180mg/L-220mg/L uses so that guarantee enough follow-up deironing and the cleaning section of copper in the said middle supernatant.
According to one embodiment of present invention, the copper content of said copper ore concentrates more than or equal to 85%, zinc content smaller or equal to 4%, cadmium content smaller or equal to 5% to guarantee the grade of said copper ore concentrates.
According to one embodiment of present invention, the treatment process of said zinc sulfate leach liquor also comprises step C): said purification slag is joined in the acid solution to utilize said acid solution that said purification slag is carried out acidleach, carry out solid-liquid separation then to reclaim metal.Through utilizing said acid solution that said purification slag is carried out acidleach, thereby the metal in the said purification slag can be reclaimed, and then the recovery of the copper in the said zinc sulfate leach liquor can be further improved.
According to one embodiment of present invention, said acid solution is the zinc electrolysis waste solution, and said acidleach was carried out 4 hours-6 hours under the condition of 70 degree-90 degree.So not only can improve the speed of said acidleach widely, and can the most of metal in the said purification slag be leached.
Additional aspect of the present invention and advantage part in the following description provide, and part will become obviously from the following description, or recognize through practice of the present invention.
Description of drawings
Above-mentioned and/or additional aspect of the present invention and advantage obviously with are easily understood becoming the description of embodiment from combining figs, wherein:
Fig. 1 is the schema according to the treatment process of the zinc sulfate leach liquor of the embodiment of the invention.
Embodiment
Describe embodiments of the invention below in detail, the example of said embodiment is shown in the drawings, and wherein identical from start to finish or similar label is represented identical or similar elements or the element with identical or similar functions.Be exemplary through the embodiment that is described with reference to the drawings below, only be used to explain the present invention, and can not be interpreted as limitation of the present invention.
In description of the invention; It will be appreciated that; Term " vertically ", " laterally ", " on ", the orientation of indications such as D score, " preceding ", " back ", " left side ", " right side ", " vertically ", " level ", " top ", " end " " interior ", " outward " or position relation be for based on orientation shown in the drawings or position relation; Only be to describe with simplifying for the ease of describing the present invention; Rather than the device or the element of indication or hint indication must have specific orientation, with specific azimuth configuration and operation, therefore can not be interpreted as limitation of the present invention.
In addition, term " first ", " second " only are used to describe purpose, and can not be interpreted as indication or hint relative importance.
In description of the invention, unless otherwise prescribed and limit, need to prove; Term " installation ", " linking to each other ", " connection " should be done broad understanding, for example, can be mechanical connection or electrical connection; Also can be the connection of two element internals, can be directly to link to each other, and also can link to each other indirectly through intermediary; For those of ordinary skill in the art, can understand the concrete implication of above-mentioned term as the case may be.
The contriver is finding through further investigation back, and in the treating processes of existing zinc sulfate leach liquor, because the neutralizing hydrolysis deironing generally carries out under pH is the condition of 5.0-5.2, about 70% cupric ion can hydrolytic precipitation gets in the slag and is removed under this pH.Cause the recovery of copper to be merely about 20% like this, caused the waste of resource.
With reference to Fig. 1 the treatment process according to the zinc sulfate leach liquor of the embodiment of the invention is described below.As shown in Figure 1, may further comprise the steps according to the treatment process of the zinc sulfate leach liquor of the embodiment of the invention:
A) zinc is joined in the zinc sulfate leach liquor to carry out replacement(metathesis)reaction, then said zinc sulfate leach liquor is carried out solid-liquid separation to obtain copper ore concentrates and middle supernatant; With
B) supernatant in said is carried out deironing and purifies to be purified slag.
According to the treatment process of the zinc sulfate leach liquor of the embodiment of the invention through removing copper in the said zinc sulfate leach liquor earlier, removing iron in the said zinc sulfate leach liquor again; Thereby not only can reclaim the most copper in the said zinc sulfate leach liquor; The recovery of copper can be reached more than 85%, and can improve the grade (bringing up to 90%) that reclaims the copper ore concentrates that obtains widely by 35%.
In some embodiments of the invention, said steps A) can may further comprise the steps:
A-1) said zinc sulfate leach liquor is filtered;
A-2) zinc is joined in the filtering said zinc sulfate leach liquor of process to carry out said replacement(metathesis)reaction; And A-3) said zinc sulfate leach liquor is carried out solid-liquid separation to obtain said copper ore concentrates and said middle supernatant.
Through before carrying out said replacement(metathesis)reaction, said zinc sulfate leach liquor being filtered, thereby can the solid impurity in the said zinc sulfate leach liquor be removed, can avoid said solid impurity to be entrained in the said copper ore concentrates like this, influence the grade of said copper ore concentrates.Preferably, the copper content of said copper ore concentrates can be more than or equal to 85%, zinc content can be smaller or equal to 4%, cadmium content can be smaller or equal to 5% to guarantee the grade of said copper ore concentrates.
Advantageously, the acid content of said zinc sulfate leach liquor can be smaller or equal to 5g/L, and the copper content of said zinc sulfate leach liquor can be more than or equal to 1000mg/L.Can avoid influencing the copper in the said zinc sulfate leach liquor of zinc dust precipitation like this because of the acid content of said zinc sulfate leach liquor is too high.
Preferably, said steps A) in, said replacement(metathesis)reaction can be carried out under the condition of 45 degree-85 degree, can improve the speed of response of said replacement(metathesis)reaction so widely.If temperature is lower than 45 degree, then the speed of response of said replacement(metathesis)reaction is slower.If temperature is higher than 85 degree, can consume then that the more energy heats but the speed of response of said replacement(metathesis)reaction can't get a promotion.
In one embodiment of the invention, said steps A) in, can said zinc sulfate leach liquor be stirred with 65 rev/mins-84 rev/mins speed when carrying out said replacement(metathesis)reaction.Zinc powder and said zinc sulfate leach liquor are mixed fully, thereby can improve the speed of response of said replacement(metathesis)reaction widely.Advantageously, said steps A) in, the reaction times of said replacement(metathesis)reaction can be 20 minutes-40 minutes.Said replacement(metathesis)reaction is carried out fully, so that the most copper in the said zinc sulfate leach liquor is cemented out.
In examples more of the present invention, the copper content of said middle supernatant can be that 180mg/L-220mg/L uses so that guarantee enough follow-up deironing and the cleaning section of copper in the said middle supernatant.
The treatment process of said zinc sulfate leach liquor can also comprise step C): can said purification slag be joined in the acid solution to utilize said acid solution that said purification slag is carried out acidleach, can carry out solid-liquid separation then to reclaim metal.Through utilizing said acid solution that said purification slag is carried out acidleach, thereby the metal in the said purification slag can be reclaimed, and then the recovery of the copper in the said zinc sulfate leach liquor can be further improved.
Advantageously, said acid solution can be that the zinc electrolysis waste solution is to reduce production costs.Said acidleach can be carried out 4 hours-6 hours under the condition of 70 degree-90 degree.So not only can improve the speed of said acidleach widely, and can the most of metal in the said purification slag be leached.
Embodiment 1
To 100m
3Acid content is that 5g/L and copper content are that the zinc sulfate leach liquor of 1000mg/L filters; Then with 150 kilograms of zinc powders join through in the filtering said zinc sulfate leach liquor so that carry out said replacement(metathesis)reaction, said replacement(metathesis)reaction is to carry out 20 minutes under 65 rev/mins the condition at 45 degree and mixing speed.Then to said zinc sulfate leach liquor carries out that solid-liquid separation is 85% to obtain copper content, zinc content is 4%, cadmium content is 5% copper ore concentrates and copper content is 220mg/L middle supernatant.Supernatant in said is carried out deironing purify slag with purifying to obtain 500 kilograms; Said purification slag is joined in the zinc electrolysis waste solution to utilize said zinc electrolysis waste solution under the condition of 70 degree, said purification slag to be carried out acidleach 4 hours, and carrying out solid-liquid separation then is 20 kilograms of 35% copper ore concentratess to obtain cupric.In this embodiment, the recovery of the copper in the said zinc sulfate leach liquor is 80%.
Embodiment 2
To 100m
3Acid content is that 4.5g/L and copper content are that the zinc sulfate leach liquor of 1100mg/L filters; Then with 165 kilograms of zinc join through in the filtering said zinc sulfate leach liquor so that carry out said replacement(metathesis)reaction, said replacement(metathesis)reaction is to carry out 30 minutes under 75 rev/mins the condition at 65 degree and mixing speed.Then to said zinc sulfate leach liquor carries out that solid-liquid separation is 87% to obtain copper content, zinc content is 3.5%, cadmium content is 4% copper ore concentrates and copper content is 200mg/L middle supernatant.Supernatant in said is carried out deironing purify slag with purifying to obtain 550 kilograms; Said purification slag is joined in the zinc electrolysis waste solution to utilize said zinc electrolysis waste solution under the condition of 80 degree, said purification slag to be carried out acidleach 5 hours, and carrying out solid-liquid separation then is 19 kilograms of 38% copper ore concentratess to obtain cupric.In this embodiment, the recovery of the copper in the said zinc sulfate leach liquor is 82%.
Embodiment 3
To 100m
3Acid content is that 4.7g/L and copper content are that the zinc sulfate leach liquor of 1200mg/L filters; Then with 180 kilograms of zinc join through in the filtering said zinc sulfate leach liquor so that carry out said replacement(metathesis)reaction, said replacement(metathesis)reaction is to carry out 40 minutes under 84 rev/mins the condition at 85 degree and mixing speed.Then to said zinc sulfate leach liquor carries out that solid-liquid separation is 90% to obtain copper content, zinc content is 3%, cadmium content is 3.6% copper ore concentrates and copper content is 180mg/L middle supernatant.Supernatant in said is carried out deironing purify slags with purifying to get 600 kilograms; Said purification slag is joined in the zinc electrolysis waste solution to utilize said zinc electrolysis waste solution under the condition of 90 degree, said purification slag to be carried out acidleach 6 hours, and carrying out solid-liquid separation then is 20 kilograms of 40% copper ore concentratess to obtain cupric.In this embodiment, the recovery of the copper in the said zinc sulfate leach liquor is 85%.
Comparative Examples
To 100m
3Acid content is that 4.7g/L and copper content are that the zinc sulfate leach liquor of 1200mg/L filters, and purifies slags to carry out deironing through filtering said zinc sulfate leach liquor with purifying to obtain 600 kilograms.Then said purification slag is joined in the zinc electrolysis waste solution to utilize said zinc electrolysis waste solution under the condition of 90 degree, said purification slag to be carried out acidleach 6 hours, carrying out solid-liquid separation then is 20 kilograms of 35% copper ore concentratess to obtain cupric.In this Comparative Examples, the copper recovery in the said zinc sulfate leach liquor is 20%, and the grade of copper is 35%.
Can find out by embodiment 1-3 and Comparative Examples; Through utilizing treatment process according to the zinc sulfate leach liquor of the embodiment of the invention; The recovery (bringing up to 85%) of the copper in the said zinc sulfate leach liquor can be improved widely, and the grade (bringing up to 90%) that reclaims the copper ore concentrates that obtains can be improved widely by 35% by 20%.
In the description of this specification sheets, the description of reference term " embodiment ", " some embodiment ", " example ", " concrete example " or " some examples " etc. means the concrete characteristic, structure, material or the characteristics that combine this embodiment or example to describe and is contained at least one embodiment of the present invention or the example.In this manual, the schematic statement to above-mentioned term not necessarily refers to identical embodiment or example.And concrete characteristic, structure, material or the characteristics of description can combine with suitable manner in any one or more embodiment or example.
Although illustrated and described embodiments of the invention; Those having ordinary skill in the art will appreciate that: under the situation that does not break away from principle of the present invention and aim, can carry out multiple variation, modification, replacement and modification to these embodiment, scope of the present invention is limited claim and equivalent thereof.
Claims (10)
1. the treatment process of a zinc sulfate leach liquor is characterized in that, may further comprise the steps:
A) zinc is joined in the zinc sulfate leach liquor to carry out replacement(metathesis)reaction, then said zinc sulfate leach liquor is carried out solid-liquid separation to obtain copper ore concentrates and middle supernatant; With
B) supernatant in said is carried out deironing and purifies to be purified slag.
2. the treatment process of zinc sulfate leach liquor according to claim 1 is characterized in that, said steps A) comprising:
A-1) said zinc sulfate leach liquor is filtered;
A-2) zinc is joined in the filtering said zinc sulfate leach liquor of process to carry out said replacement(metathesis)reaction; With
A-3) said zinc sulfate leach liquor is carried out solid-liquid separation to obtain said copper ore concentrates and said middle supernatant.
3. the treatment process of zinc sulfate leach liquor according to claim 1 is characterized in that, said steps A) in, the acid content of said zinc sulfate leach liquor smaller or equal to 5g/L and copper content more than or equal to 1000mg/L.
4. the treatment process of zinc sulfate leach liquor according to claim 1 is characterized in that, said steps A) in, said replacement(metathesis)reaction is carried out under the condition of 45 degree-85 degree.
5. the treatment process of zinc sulfate leach liquor according to claim 4 is characterized in that, said steps A) in, the reaction times of said replacement(metathesis)reaction is 20 minutes-40 minutes.
6. the treatment process of zinc sulfate leach liquor according to claim 5 is characterized in that, said steps A) in, the speed with 65 rev/mins-84 rev/mins when carrying out said replacement(metathesis)reaction stirs said zinc sulfate leach liquor.
7. the treatment process of zinc sulfate leach liquor according to claim 1 is characterized in that, the copper content of said middle supernatant is 180mg/L-220mg/L.
8. the treatment process of zinc sulfate leach liquor according to claim 1 is characterized in that, the copper content of said copper ore concentrates more than or equal to 85%, zinc content smaller or equal to 4%, cadmium content is smaller or equal to 5%.
9. the treatment process of zinc sulfate leach liquor according to claim 1 is characterized in that, also comprises step C): said purification slag is joined in the acid solution to utilize said acid solution that said purification slag is carried out acidleach, carry out solid-liquid separation then to reclaim metal.
10. the treatment process of zinc sulfate leach liquor according to claim 9 is characterized in that, said acid solution is the zinc electrolysis waste solution, and said acidleach was carried out 4 hours-6 hours under the condition of 70 degree-90 degree.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102899491A (en) * | 2012-10-12 | 2013-01-30 | 中南大学 | Method for floating and separating high-concentration iron ions from zinc sulfate leachate |
| CN103721851A (en) * | 2013-12-30 | 2014-04-16 | 云南罗平锌电股份有限公司 | Method for recycling zinc, lead, silver and copper from zinc oxide ore |
| CN106756025A (en) * | 2016-11-29 | 2017-05-31 | 湖南水口山有色金属集团有限公司 | A kind of method of impurity in utilization purification slag of zinc hydrometallurgy removing oxidation zinc lixiviating solution |
| CN110484736A (en) * | 2019-09-29 | 2019-11-22 | 湖南仁发材料科技有限公司 | A method of copper removal is purified for zinc sulfate leaching liquid |
| CN110819801A (en) * | 2018-08-07 | 2020-02-21 | 昆明理工大学 | Method for purifying zinc sulfate solution by microwave heating of zinc powder |
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| CN86108798A (en) * | 1986-12-30 | 1988-08-03 | 戴元宁 | The full wet method of zinc ore is produced zinc sulfate and active zinc flower |
| CN1530452A (en) * | 2003-03-14 | 2004-09-22 | 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 |
| CN101407862A (en) * | 2008-11-28 | 2009-04-15 | 株洲冶炼集团股份有限公司 | Method for previously removing copper from copper-containing solution |
| CN102071318A (en) * | 2011-01-25 | 2011-05-25 | 云南冶金集团股份有限公司 | Purification method of zinc sulfate leaching liquid |
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2012
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| CN86108798A (en) * | 1986-12-30 | 1988-08-03 | 戴元宁 | The full wet method of zinc ore is produced zinc sulfate and active zinc flower |
| CN1530452A (en) * | 2003-03-14 | 2004-09-22 | 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 |
| CN101407862A (en) * | 2008-11-28 | 2009-04-15 | 株洲冶炼集团股份有限公司 | Method for previously removing copper from copper-containing solution |
| CN102071318A (en) * | 2011-01-25 | 2011-05-25 | 云南冶金集团股份有限公司 | Purification method of zinc sulfate leaching liquid |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102899491A (en) * | 2012-10-12 | 2013-01-30 | 中南大学 | Method for floating and separating high-concentration iron ions from zinc sulfate leachate |
| CN102899491B (en) * | 2012-10-12 | 2013-12-04 | 中南大学 | Method for floating and separating high-concentration iron ions from zinc sulfate leachate |
| CN103721851A (en) * | 2013-12-30 | 2014-04-16 | 云南罗平锌电股份有限公司 | Method for recycling zinc, lead, silver and copper from zinc oxide ore |
| CN103721851B (en) * | 2013-12-30 | 2017-05-10 | 云南罗平锌电股份有限公司 | Method for recycling zinc, lead, silver and copper from zinc oxide ore |
| CN106756025A (en) * | 2016-11-29 | 2017-05-31 | 湖南水口山有色金属集团有限公司 | A kind of method of impurity in utilization purification slag of zinc hydrometallurgy removing oxidation zinc lixiviating solution |
| CN110819801A (en) * | 2018-08-07 | 2020-02-21 | 昆明理工大学 | Method for purifying zinc sulfate solution by microwave heating of zinc powder |
| CN110819801B (en) * | 2018-08-07 | 2021-01-22 | 昆明理工大学 | Method for purifying zinc sulfate solution by microwave heating of zinc powder |
| CN110484736A (en) * | 2019-09-29 | 2019-11-22 | 湖南仁发材料科技有限公司 | A method of copper removal is purified for zinc sulfate leaching liquid |
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Application publication date: 20120919 |