CN105400955A - Method for removing copper ions in zinc sulfate solution - Google Patents
Method for removing copper ions in zinc sulfate solution Download PDFInfo
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- CN105400955A CN105400955A CN201510802755.8A CN201510802755A CN105400955A CN 105400955 A CN105400955 A CN 105400955A CN 201510802755 A CN201510802755 A CN 201510802755A CN 105400955 A CN105400955 A CN 105400955A
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- Prior art keywords
- zinc sulfate
- solution
- cupric
- cupric ion
- ammonium bisulfite
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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
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
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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
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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
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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
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- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Geology (AREA)
- Removal Of Specific Substances (AREA)
Abstract
The invention provides a method for removing copper ions in a zinc sulfate solution. According to the method, ammonium hydrogen sulfite is used as a reducing agent for removing the copper ions in the zinc sulfate solution, the PH value of the zinc sulfate solution is 4.0-4.5, and the concentration of the copper ions in the zinc sulfate solution is 1-10 g/L. The method specifically comprises the following steps that the zinc sulfate solution is added into a reaction tank and is heated up to 45-55 DEG C; ammonium hydrogen sulfite is added for reaction, the reaction time is 25-30 min, and the reaction temperature is 45-55 DEG C; the copper ions in the zinc sulfate solution are changed to be in a cuprous oxide form from a bivalence form and are separated from the zinc sulfate solution; solid-liquid separation is conducted after reaction is completed, and the zinc sulfate solution without the copper ions and copper-bearing filter residues are obtained.
Description
Technical field
The present invention relates to a kind of chemical technology field, particularly a kind of method removing cupric ion in solution of zinc sulfate.
Background technology
At present, the ordinary method removing cupric ion in solution of zinc sulfate is a lot, as zinc powder reduction method, extraction process etc.Zinc powder reduction method adds in the solution of zinc sulfate of copper ions by zinc powder, copper ions in solution of zinc sulfate removed by displacement.Extraction process is by adding phosphoric acid dibutyl ester in the solution of zinc sulfate of copper ions, copper ions in solution of zinc sulfate is extracted by phosphoric acid dibutyl ester.
The treating processes of aforesaid method is very complicated, and cost is very high, and effect is not very good, also can produce reluctant copper-cadmium slag.
Summary of the invention
The object of the invention is to overcome the above-mentioned deficiency of prior art and a kind of method removing cupric ion in solution of zinc sulfate is provided.
Technical scheme of the present invention is: a kind of method removing cupric ion in solution of zinc sulfate, it is employing ammonium bisulfite removes in solution of zinc sulfate cupric ion as reductive agent, pH value in solution of zinc sulfate is 4.0 ~ 4.5, and in solution of zinc sulfate, the concentration of cupric ion is 1 ~ 10g/L.
Its concrete steps are as follows:
A, solution of zinc sulfate is added in retort;
B, the solution of zinc sulfate in retort is warming up to 45 ~ 55 DEG C;
C, in retort, add ammonium bisulfite, reduce bivalent cupric ion in solution of zinc sulfate with ammonium bisulfite as reductive agent, 1m
3solution of zinc sulfate add the ammonium bisulfite of 5.1 ~ 49.9Kg, the mol ratio of ammonium bisulfite and cupric ion is 3.2 ~ 3.3, reaction times is 25 ~ 30min, temperature of reaction is 45 ~ 55 DEG C, make cupric ion in solution of zinc sulfate become Red copper oxide form by divalence, be separated from solution of zinc sulfate;
The chemical equation of ammonium bisulfite and solution of zinc sulfate is as follows:
6(NH4)HSO3+2CuSO4=3(NH4)2SO4+3H2O+5SO2↑+Cu2O
Reducing heavy copper with other reductive agent is liquid and gas soluble in water unlike the reduzate of ammonium bisulfite;
D, reaction carry out solid-liquid separation after terminating, and obtain solution of zinc sulfate and the cupric filter residue of removing cupric ion, and the solution of zinc sulfate of removing cupric ion enters subsequent processing purifying regeneration and produces zinc series product;
E, the cupric filter residue feeding washery slag tank will acquired in step D, in washery slag tank, add water, the solid-to-liquid ratio of cupric filter residue and water is 1:3, then adds the vitriol oil and regulates pH value to 3.5 ~ 4.0, carry out solid-liquor separation after stirring 25 ~ 30min, obtain the copper sludge filter residue that cupric is of high grade.
The present invention compared with prior art has following features:
1, adopt ammonium bisulfite to remove cupric ion in solution of zinc sulfate as reductive agent, copper removal effective, the residual copper concentration of solution of zinc sulfate all lower than 0.05g/L, can output copper grade higher than the Red copper oxide of 80%, be beneficial to the recovery of copper;
2, the copper removal operating time is short, and compared with the method for the copper removal industrially used with other, its cost is low, is easy to combine with existing zinc wet process, comprehensively achieves economic benefit and environmental benefit.
Below in conjunction with embodiment, detailed construction of the present invention is further described.
Embodiment
Embodiment one, a kind of method removing cupric ion in solution of zinc sulfate, it is employing ammonium bisulfite removes in solution of zinc sulfate cupric ion as reductive agent, and the pH value in solution of zinc sulfate is 4.0, and in solution of zinc sulfate, the concentration of cupric ion is 1g/L.
Its concrete steps are as follows:
A, solution of zinc sulfate is added in retort;
B, the solution of zinc sulfate in retort is warming up to 45 DEG C;
C, in retort, add ammonium bisulfite, reduce bivalent cupric ion in solution of zinc sulfate with ammonium bisulfite as reductive agent, 1m
3solution of zinc sulfate add the ammonium bisulfite of 5.1Kg, the mol ratio of ammonium bisulfite and cupric ion is 3.2, and the reaction times is 25min, and temperature of reaction is 45 DEG C, make cupric ion in solution of zinc sulfate become Red copper oxide form by divalence, be separated from solution of zinc sulfate;
The chemical equation of ammonium bisulfite and solution of zinc sulfate is as follows:
6(NH4)HSO3+2CuSO4=3(NH4)2SO4+3H2O+5SO2↑+Cu2O
Reducing heavy copper with other reductive agent is liquid and gas soluble in water unlike the reduzate of ammonium bisulfite;
D, reaction carry out solid-liquid separation after terminating, and obtain solution of zinc sulfate and the cupric filter residue of removing cupric ion, and the solution of zinc sulfate of removing cupric ion enters subsequent processing purifying regeneration and produces zinc series product;
E, the cupric filter residue feeding washery slag tank will acquired in step D, in washery slag tank, add water, the solid-to-liquid ratio of cupric filter residue and water is 1:3, then adds the vitriol oil and regulates pH value to 3.5, carry out solid-liquor separation, obtain the copper sludge filter residue that cupric is of high grade after stirring 25min.
After testing, adopt the present invention to remove cupric ion in solution of zinc sulfate, in the solution of zinc sulfate processed, cupric ion is 0.03g/L, and copper sludge filter residue cupric 81%, copper removal effect is very good.
Embodiment two, a kind of method removing cupric ion in solution of zinc sulfate, it is employing ammonium bisulfite removes in solution of zinc sulfate cupric ion as reductive agent, and the pH value in solution of zinc sulfate is 4.25, and in solution of zinc sulfate, the concentration of cupric ion is 5g/L.
Its concrete steps are as follows:
A, solution of zinc sulfate is added in retort;
B, the solution of zinc sulfate in retort is warming up to 50 DEG C;
C, in retort, add ammonium bisulfite, reduce bivalent cupric ion in solution of zinc sulfate with ammonium bisulfite as reductive agent, 1m
3solution of zinc sulfate add the ammonium bisulfite of 25.3Kg, the mol ratio of ammonium bisulfite and cupric ion is 3.25, and the reaction times is 28min, and temperature of reaction is 50 DEG C, make cupric ion in solution of zinc sulfate become Red copper oxide form by divalence, be separated from solution of zinc sulfate;
The chemical equation of ammonium bisulfite and solution of zinc sulfate is as follows:
6(NH4)HSO3+2CuSO4=3(NH4)2SO4+3H2O+5SO2↑+Cu2O
Reducing heavy copper with other reductive agent is liquid and gas soluble in water unlike the reduzate of ammonium bisulfite;
D, reaction carry out solid-liquid separation after terminating, and obtain solution of zinc sulfate and the cupric filter residue of removing cupric ion, and the solution of zinc sulfate of removing cupric ion enters subsequent processing purifying regeneration and produces zinc series product;
E, the cupric filter residue feeding washery slag tank will acquired in step D, in washery slag tank, add water, the solid-to-liquid ratio of cupric filter residue and water is 1:3, then adds the vitriol oil and regulates pH value to 3.75, carry out solid-liquor separation, obtain the copper sludge filter residue that cupric is of high grade after stirring 30min.
After testing, adopt the present invention to remove cupric ion in solution of zinc sulfate, in the solution of zinc sulfate processed, cupric ion is 0.04g/L, and copper sludge filter residue cupric 81%, copper removal effect is very good.
Embodiment three, a kind of method removing cupric ion in solution of zinc sulfate, it is employing ammonium bisulfite removes in solution of zinc sulfate cupric ion as reductive agent, and the pH value in solution of zinc sulfate is 4.5, and in solution of zinc sulfate, the concentration of cupric ion is 10g/L.
Its concrete steps are as follows:
A, solution of zinc sulfate is added in retort;
B, the solution of zinc sulfate in retort is warming up to 55 DEG C;
C, in retort, add ammonium bisulfite, reduce bivalent cupric ion in solution of zinc sulfate with ammonium bisulfite as reductive agent, 1m
3solution of zinc sulfate add the ammonium bisulfite of 49.9Kg, the mol ratio of ammonium bisulfite and cupric ion is 3.3, and the reaction times is 30min, and temperature of reaction is 55 DEG C, make cupric ion in solution of zinc sulfate become Red copper oxide form by divalence, be separated from solution of zinc sulfate;
The chemical equation of ammonium bisulfite and solution of zinc sulfate is as follows:
6(NH4)HSO3+2CuSO4=3(NH4)2SO4+3H2O+5SO2↑+Cu2O
Reducing heavy copper with other reductive agent is liquid and gas soluble in water unlike the reduzate of ammonium bisulfite;
D, reaction carry out solid-liquid separation after terminating, and obtain solution of zinc sulfate and the cupric filter residue of removing cupric ion, and the solution of zinc sulfate of removing cupric ion enters subsequent processing purifying regeneration and produces zinc series product;
E, the cupric filter residue feeding washery slag tank will acquired in step D, in washery slag tank, add water, the solid-to-liquid ratio of cupric filter residue and water is 1:3, then adds the vitriol oil and regulates pH value to 4.0, carry out solid-liquor separation, obtain the copper sludge filter residue that cupric is of high grade after stirring 30min.
After testing, adopt the present invention to remove cupric ion in solution of zinc sulfate, in the solution of zinc sulfate processed, cupric ion is 0.035g/L, and copper sludge filter residue cupric 81.2%, copper removal effect is very good.
Claims (1)
1. remove the method for cupric ion in solution of zinc sulfate for one kind, it is characterized in that: it is employing ammonium bisulfite removes in solution of zinc sulfate cupric ion as reductive agent, pH value in solution of zinc sulfate is 4.0 ~ 4.5, and in solution of zinc sulfate, the concentration of cupric ion is 1 ~ 10g/L;
Its concrete steps are as follows:
A, solution of zinc sulfate is added in retort;
B, the solution of zinc sulfate in retort is warming up to 45 ~ 55 DEG C;
C, in retort, add ammonium bisulfite, reduce bivalent cupric ion in solution of zinc sulfate with ammonium bisulfite as reductive agent, 1m
3solution of zinc sulfate add the ammonium bisulfite of 5.1 ~ 49.9Kg, the mol ratio of ammonium bisulfite and cupric ion is 3.2 ~ 3.3, reaction times is 20 ~ 30min, temperature of reaction is 45 ~ 55 DEG C, make cupric ion in solution of zinc sulfate become Red copper oxide form by divalence, be separated from solution of zinc sulfate;
The chemical equation of ammonium bisulfite and solution of zinc sulfate is as follows:
6(NH4)HSO3+2CuSO4=3(NH4)2SO4+3H2O+5SO2↑+Cu2O
Reducing heavy copper with other reductive agent is liquid and gas soluble in water unlike the reduzate of ammonium bisulfite;
D, reaction carry out solid-liquid separation after terminating, and obtain solution of zinc sulfate and the cupric filter residue of removing cupric ion, and the solution of zinc sulfate of removing cupric ion enters subsequent processing purifying regeneration and produces zinc series product;
E, the cupric filter residue feeding washery slag tank will acquired in step D, in washery slag tank, add water, the solid-to-liquid ratio of cupric filter residue and water is 1:3, then adds the vitriol oil and regulates pH value to 3.5 ~ 4.0, carry out solid-liquor separation after stirring 25 ~ 30min, obtain the copper sludge filter residue that cupric is of high grade.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510802755.8A CN105400955A (en) | 2015-11-19 | 2015-11-19 | Method for removing copper ions in zinc sulfate solution |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510802755.8A CN105400955A (en) | 2015-11-19 | 2015-11-19 | Method for removing copper ions in zinc sulfate solution |
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| CN105400955A true CN105400955A (en) | 2016-03-16 |
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| CN201510802755.8A Pending CN105400955A (en) | 2015-11-19 | 2015-11-19 | Method for removing copper ions in zinc sulfate solution |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106191441A (en) * | 2016-08-05 | 2016-12-07 | 来宾华锡冶炼有限公司 | A kind of method preparing solution of zinc sulfate removing impurities agent |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2280168A (en) * | 1941-08-22 | 1942-04-21 | Jr William B Stoddard | Process of preparing cuprous oxide |
| CN1054956A (en) * | 1990-03-12 | 1991-10-02 | 烟台市古现化工厂 | A kind of method of producing Red copper oxide |
| JP2006069879A (en) * | 2004-09-06 | 2006-03-16 | Fuji Photo Film Co Ltd | Method of manufacturing cuprous oxide particles, and cuprous oxide particles |
| CN102390861A (en) * | 2011-08-17 | 2012-03-28 | 金川集团有限公司 | Method for preparing cuprous oxide powder |
| CN103112883A (en) * | 2012-12-10 | 2013-05-22 | 浙江理工大学 | Method for preparing superfine cuprous oxide powder |
| CN104591257A (en) * | 2015-01-12 | 2015-05-06 | 广东光华科技股份有限公司 | Preparation method of cubic micro/nano cuprous oxide powder |
-
2015
- 2015-11-19 CN CN201510802755.8A patent/CN105400955A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2280168A (en) * | 1941-08-22 | 1942-04-21 | Jr William B Stoddard | Process of preparing cuprous oxide |
| CN1054956A (en) * | 1990-03-12 | 1991-10-02 | 烟台市古现化工厂 | A kind of method of producing Red copper oxide |
| JP2006069879A (en) * | 2004-09-06 | 2006-03-16 | Fuji Photo Film Co Ltd | Method of manufacturing cuprous oxide particles, and cuprous oxide particles |
| CN102390861A (en) * | 2011-08-17 | 2012-03-28 | 金川集团有限公司 | Method for preparing cuprous oxide powder |
| CN103112883A (en) * | 2012-12-10 | 2013-05-22 | 浙江理工大学 | Method for preparing superfine cuprous oxide powder |
| CN104591257A (en) * | 2015-01-12 | 2015-05-06 | 广东光华科技股份有限公司 | Preparation method of cubic micro/nano cuprous oxide powder |
Non-Patent Citations (1)
| Title |
|---|
| 杨加定: ""电镀污泥中铜、镍、铬、锌的回收利用研究"", 《化学工程与装备》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106191441A (en) * | 2016-08-05 | 2016-12-07 | 来宾华锡冶炼有限公司 | A kind of method preparing solution of zinc sulfate removing impurities agent |
| CN106191441B (en) * | 2016-08-05 | 2017-11-03 | 来宾华锡冶炼有限公司 | A kind of method for preparing solution of zinc sulfate removing impurities agent |
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Application publication date: 20160316 |
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