CN106435206A - Method for removing chlorine in copper sulfate solution by copper refining slag - Google Patents
Method for removing chlorine in copper sulfate solution by copper refining slag Download PDFInfo
- Publication number
- CN106435206A CN106435206A CN201611152711.6A CN201611152711A CN106435206A CN 106435206 A CN106435206 A CN 106435206A CN 201611152711 A CN201611152711 A CN 201611152711A CN 106435206 A CN106435206 A CN 106435206A
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- Prior art keywords
- copper
- chlorine
- refining slag
- slag
- bath
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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
- C22B7/007—Wet processes by acid leaching
-
- 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
-
- 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
- C22B7/04—Working-up slag
-
- 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)
- Mechanical Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a method for removing chlorine in a copper sulfate solution by copper refining slag. The method for removing the chlorine in the copper sulfate solution by the copper refining slag comprises the following steps that the copper refining slag is smashed, ball-milled to a certain particle size, and then added into the copper sulfate solution containing the chlorine; and sub copper and chlorine ions in the copper refining slag are formed into cuprous chloride which is insoluble in acid, and after the cuprous chloride is filtered by a plate-and-frame press filter, a low chloride copper sulfate solution is obtained. The method can be widely used for removing the chlorine ions of all kinds of concentrations in the copper sulfate solution, the steps are easy, and operation is simple and convenient; the sources of antichlor are wide, production cost is low, secondary pollution is not generated in the whole production process, and chlorine removing slag can be returned to conduct fire melting to extract copper.
Description
Technical field
The present invention relates to non-ferrous metal field of hydrometallurgy, chlorine in particularly a kind of copper refining slag removing copper-bath
Method.
Background technology
Copper refining slag is the slag that blister copper or copper scrap produce during removing impurities by oxidation and reduction refining copper.Due to blister copper
Or containing the impurity that Fe, Pb, Zn, Ni, As, Sb, Sn, Sb etc. are oxidizable in copper scrap, these oxides are more stable than Red copper oxide,
And there is the low characteristic of fusing degree, in removing impurities by oxidation process, stove is formed on copper liquid surface with the form of oxide for this these impurity
Slag.Therefore in copper refining slag except copper with the forms such as Cu2O, metallic copper, cupric silicate and ferrous acid copper presence in addition to, also contain lead,
The compounds such as stannum, arsenic, antimony, zinc, nickel, cobalt.Copper refining Copper in Slag is very high and contains other metals, so must recycle.One
As copper refining slag return as cold burden and bessemerize, or allocate concentrate into and send into blast furnace or reverberatory smelting.
In the hydrometallurgy of copper, chlorine strictly controls Chlorine in Solution ion concentration as a kind of element harmful to electrolysis.
When chloride ion is higher than 200mg/L, positive plate corrosion failure often occurs, guiding discharge is uneven, so that tough cathode is sent out
Embrittlement produces copper granule not of uniform size, and when serious, minus plate goes out one layer of white suspension thing of attachment during groove.
In copper-bath, dechlorination method is more, mainly by the AgCl sedimentation method, electrolysis, ion exchange, bismuth oxide method,
The AgCl sedimentation method are directed in copper-bath add silver sulfate, generate the silver nitride precipitation being insoluble in acid, the method operation letter
Single, dechlorination effect is good, but reagent consumes composition height, is not suitable for industrial practice.
Electrolysis is the chlorine-resistant corrosivity using coated titanium anode, so that chloride ion is given birth in anode discharge under electric field action
Become chlorine thus removing the chloride ion in solution, to the removing of low-level chlorinated ion effectively, chlorine ion concentration is higher than 1g/L to the method
Solution dechlorination when groove face air pole poor, now separate out tough cathode almost shapeless.
Ion exchange is the characteristic using anion exchange resin selective absorption Chlorine in Solution ion, will from solution
The method that chloride ion adsorbs and removes.The exchanger resin adsorption capacity that this method is used is low, easy leakage, the copper sulfate of slightly higher concentration
Solution lead to after crystallizing in resin resin regeneration is difficult, regenerate low concentration chlorine-contained wastewater cannot internal consumption, regeneration
The processes composition of water is high.
Content of the invention
The invention aims to effectively in removing copper-bath chlorine, provide a kind of using enterprise's self-produced copper essence
The method that refining slag carries out dechlorination.
To achieve these goals, the technical solution used in the present invention is：
The self-produced copper refining slag of copper smelting plant, usual cupric 40-50% about, the main thing phase of this copper is Red copper oxide, also few
Amount copper and copper oxide.When copper refining slag puts into the copper-bath containing necessarily acid, Red copper oxide is entered in solution by sulfuric acid leaching,
In solution, cuprous ion and chloride ion form the Cu-lyt. precipitation being insoluble in acid.Elemental copper in copper refining slag and copper ion with
Chloride ion also can form Cu-lyt. precipitation.
Concretely comprise the following steps：（1）By copper refining slag through crushing, being milled to certain particle size, copper refining Copper in Slag mass percent
For 40% about；（2）Step is added in copper-bath（1）Gained copper refining slag, is warming up to 65-70 DEG C of stirring reaction 60min
After filter, filter initial stage resulting solution more muddy, need to again filter treat filtrate clarification can put into storage tank；（3）Copper refining slag adds
Enter 4-6 times that amount is chlorine ions in copper-bath, copper-bath chlorinity is reduced to below 100mg/L.
Whole reaction mechanism is as follows：
Cu2O+H2SO4=Cu2SO4+H2O
CuO+H2SO4=CuSO4+H2O
Cu++Cl-=CuCl↓
Cu+Cu2++2Cl-=2CuCl↓
Beneficial effects of the present invention：
（1）Chlorine in copper refining slag removing copper-bath, can process the copper-bath in 0.1-10g/L for the chloride ion, only need to close
Suitable addition, in copper-bath, chlorine ion concentration all can be reduced to 100mg/L.
（2）Step of the present invention is simple, easy and simple to handle, antichlor wide material sources, low production cost, and whole production will not produce
Secondary pollution, dechlorination slag can return to pyrometallurgical smelting and carries copper.
Brief description
Fig. 1 is the process chart of the present invention.
Specific embodiment
The self-produced copper refining slag of copper smelting plant, usual cupric 40-50% about, the main thing phase of this copper is Red copper oxide, also
There are a small amount of copper and copper oxide.When copper refining slag puts into the copper-bath containing necessarily acid, Red copper oxide is entered molten by sulfuric acid leaching
In liquid, in solution, cuprous ion and chloride ion form the Cu-lyt. precipitation being insoluble in acid.Elemental copper in copper refining slag and copper
Ion and chloride ion also can form Cu-lyt. precipitation.
As shown in figure 1, the method that copper refining slag removes chlorine in copper-bath, it comprises the steps of：
（1）By copper refining slag through crushing, being milled to certain particle size, copper refining Copper in Slag mass percent is 40% about；
（2）Step is added in copper-bath（1）Gained copper refining slag, is warming up to 65-70 DEG C of stirring reaction 60min；
（3）Solid-liquid separation:The slip that upper step is produced is filtered by filter press, and filtration initial stage resulting solution is more muddy, needs
Again filter and treat that filtrate clarification can put into storage tank, output low sulfuric chlorohydrin copper solution and white cuprous salt precipitate.
Wherein, contain chloride ion in copper-bath solution, chlorine ion concentration is 0.1-10g/L.
Specific embodiment is as follows：
Embodiment one：
Certain copper sulfate leaching liquid composition is shown in Table 1.
Table 1 copper sulfate leaching liquid（g/L）
| Project | H2SO4 | Cu | Cl |
| Copper sulfate leaching liquid | 91.46 | 83.79 | 3.65 |
（1）Copper refining slag is crushed, was milled to 120 mesh, copper refining slag（Butt）Copper content 39.95%.
（2）In copper sulfate leaching liquid, Cl concentration is 3.65g/L, and volume 1L adds step（1）Gained refining slag 18.2g, molten
Liquid is warming up to sucking filtration after 65-70 DEG C of stirring reaction 60min, the chloride 50mg/L of filtrate.
Embodiment two
Certain copper ammonium acetate is shown in Table 2.
Table 2 bronze medal leachate（g/L）
| Project | H2SO4 | Cu | Cl |
| Copper sulfate leaching liquid | 94.39 | 75.6 | 2.92 |
（1）Copper refining slag is crushed, was milled to 200 mesh, copper refining slag（Wet basis）Copper content 40.18%；
（2）In copper sulfate leaching liquid, Cl concentration is 2.92g/L, and volume 1L adds step（1）Gained refining slag（Wet basis）
17.52g, solution is warming up to sucking filtration after 65-70 DEG C of stirring reaction 60min, the chloride 100mg/L of filtrate.
Chlorine in copper refining slag removing copper-bath, can process the copper-bath in 0.1-10g/L for the chloride ion, only need to close
Suitable addition, in copper-bath, chlorine ion concentration all can be reduced to 100mg/L.
Step of the present invention is simple, easy and simple to handle, antichlor wide material sources, low production cost, and whole production will not produce two
Secondary pollution, dechlorination slag can return to pyrometallurgical smelting and carries copper.
Ultimate principle, principal character and the advantages of the present invention of the present invention have been shown and described above.The technology of the industry
The simply present invention it should be appreciated that the present invention is not restricted to the described embodiments, described in above-described embodiment and description for the personnel
Principle, without departing from the spirit and scope of the present invention the present invention also have various changes and modifications, these change and
Improvement both falls within the range of claimed invention.The protection domain of application claims by appending claims and its
Equivalent defines.
Claims (3)
1. a kind of copper refining slag removes the method for chlorine in copper-bath it is characterised in that it comprises the steps of：
（1）By copper refining slag through crushing, being milled to certain particle size, copper refining Copper in Slag mass percent is 40% about；
（2）Step is added in copper-bath（1）Gained copper refining slag, is warming up to 65-70 DEG C of stirring reaction 60min；
（3）Solid-liquid separation:The slip that upper step is produced is filtered by filter press, 65-70 DEG C of filtration temperature, filters initial stage institute
Solution is more muddy, need to again filter and treat that filtrate clarification can put into storage tank, output low sulfuric chlorohydrin copper solution and white cuprous salt
Precipitation.
2. a kind of copper refining slag removes the method for chlorine in copper-bath it is characterised in that described sulfur according to claim 1
Chloride ion, chlorine ion concentration 0.1-10g/L is contained in sour copper solution solution.
3. according to claim 1 a kind of copper refining slag remove chlorine in copper-bath method it is characterised in that, copper refining
In slag, copper component is Red copper oxide and elemental copper, copper content 40%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611152711.6A CN106435206A (en) | 2016-12-14 | 2016-12-14 | Method for removing chlorine in copper sulfate solution by copper refining slag |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611152711.6A CN106435206A (en) | 2016-12-14 | 2016-12-14 | Method for removing chlorine in copper sulfate solution by copper refining slag |
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| CN106435206A true CN106435206A (en) | 2017-02-22 |
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| CN201611152711.6A Pending CN106435206A (en) | 2016-12-14 | 2016-12-14 | Method for removing chlorine in copper sulfate solution by copper refining slag |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109536720A (en) * | 2018-12-17 | 2019-03-29 | 广州科城环保科技有限公司 | The removal methods of chlorine in a kind of copper-bath |
| CN112540162A (en) * | 2020-11-25 | 2021-03-23 | 江苏雅信昆成检测科技有限公司 | Water quality biotoxicity detection method |
| CN113060754A (en) * | 2021-03-16 | 2021-07-02 | 江苏理工学院 | Doped cuprous dechlorinating agent and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101113015A (en) * | 2007-07-13 | 2008-01-30 | 株洲冶炼集团股份有限公司 | Method for removing chlorine from zinc sulfate solution |
| CN104046793A (en) * | 2014-06-27 | 2014-09-17 | 湖南水口山有色金属集团有限公司 | Method of removing chlorine in zinc sulfate solution |
| CN105671313A (en) * | 2014-11-17 | 2016-06-15 | 西安瑞凯电力科技有限公司 | Method for removing chloride ions in copper sulphate solution |
-
2016
- 2016-12-14 CN CN201611152711.6A patent/CN106435206A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101113015A (en) * | 2007-07-13 | 2008-01-30 | 株洲冶炼集团股份有限公司 | Method for removing chlorine from zinc sulfate solution |
| CN104046793A (en) * | 2014-06-27 | 2014-09-17 | 湖南水口山有色金属集团有限公司 | Method of removing chlorine in zinc sulfate solution |
| CN105671313A (en) * | 2014-11-17 | 2016-06-15 | 西安瑞凯电力科技有限公司 | Method for removing chloride ions in copper sulphate solution |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109536720A (en) * | 2018-12-17 | 2019-03-29 | 广州科城环保科技有限公司 | The removal methods of chlorine in a kind of copper-bath |
| CN112540162A (en) * | 2020-11-25 | 2021-03-23 | 江苏雅信昆成检测科技有限公司 | Water quality biotoxicity detection method |
| CN113060754A (en) * | 2021-03-16 | 2021-07-02 | 江苏理工学院 | Doped cuprous dechlorinating agent and preparation method and application thereof |
| CN113060754B (en) * | 2021-03-16 | 2021-10-19 | 江苏理工学院 | Doped cuprous dechlorinating agent and preparation method and application thereof |
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Application publication date: 20170222 |