CN103526230A - Method for producing high-quality cathode copper with high efficiency in copper electrolyte purification process - Google Patents
Method for producing high-quality cathode copper with high efficiency in copper electrolyte purification process Download PDFInfo
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- CN103526230A CN103526230A CN201310462351.XA CN201310462351A CN103526230A CN 103526230 A CN103526230 A CN 103526230A CN 201310462351 A CN201310462351 A CN 201310462351A CN 103526230 A CN103526230 A CN 103526230A
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Abstract
The invention discloses a method for producing high-quality cathode copper with high efficiency in copper electrolyte purification process. The method comprises steps: first, a copper sulphate mother liquid, an electrolyte and a copper-containing waste liquid are stored in a liquid collection tank to form a copper removing front liquid; second, the copper removing front liquid is transported from the liquid collection tank to a low tank with a flow of Q supplement and then mixed with an electrodeposition circulation liquid in the low tank; third, the premixed copper removing front liquid and electrodeposition circulation liquid are heated through a plate heat exchanger with a controlled temperature of 30DEG C-70 DEG C and then are sent to a high tank, distributed to copper removing tanks by the high tank and then subjected to one-section electrodeposition copper removal; fourth, part of the copper removing back liquid after the one-section electrodeposition copper removal is sent back to the one-section low tank through a liquid return pipe which is communicated with each copper removing tank, the other part of the copper removing back liquid with a flow of Q output is transported to the next process, and the Q output is equal to the Q supplement. Through smaller modification, the aim of production of high-quality cathode copper is achieved.
Description
Technical field
The present invention relates to the electro-deposition techniques of copper metal in hydrometallurgy process solution, especially, in cleaning copper electrolyte removal of impurities process, remove the method for copper in electrolytic solution.
Background technology
In existing cleaning copper electrolyte impurity removing technology, industrial most widely used be still to utilize insoluble anode electrodeposition method to remove copper and arsenic in electrolytic solution, antimony, bismuth etc., through years of researches and improvement, developed multiple electrodeposition method for decoppering: be interrupted electrodeposition method, continuous electrodeposition method (inducing dearsenification method), limit current density method, control cathode potential method, eddy flow electrodeposition method;
These methods are mainly for electrodeposition decopper(ing), to produce the rate of recovery that arsine gas worsens production environment and improve antimony, bismuth, nickel etc. in electrolytic solution latter stage to have more research.But relatively less for the research that improves cathode copper quality product in purifying decopper(ing) process.
Be interrupted electrodeposition method, also referred to as one section of decopper(ing) method, conventional in some middle-size and small-size factories.This method is that the solution of cupric and impurity is placed in electrolyzer, disposable by its electrodeposition to copper, degree that arsenic concentration is lower.In the electrodeposition later stage, the high copper sponge of impurity that arsenic, antimony, bismuth and copper are separated out generation at negative electrode returns to the smelting system of pyrogenic process, causes the vicious cycle in whole system of the impurity such as arsenic on the one hand, has increased on the other hand processing cost.
Continuous decopper(ing) dearsenification electrodeposition method, also referred to as revulsion dearsenification.Within 1980, by SUMITOMO CHEMICAL metal mine Co., Ltd., invented, and within 1985, introduce China, the purification system of application and more domestic large-scale cupric electrolysis factories, has obtained good effect.Revulsion mainly, by supplementing assisted solution, keeps copper, arsonium ion in certain concentration range, to realize the maximum removal efficiency of arsenic, and control the generation of arsine gas.This method is more paid attention to removing of arsenic, though can produce tabular electrolytic copper in front several copper liberation cells, is conventionally subject to the constraint of whole system processing condition, tabular electrolytic copper also often impure element compared with high and directly return smelting system.
Limit current density method, the hydrogen arsenide that this kind of method produces decopper(ing) latter stage has good control, and the efficiency of dearsenification is also higher, but current density is less, and can not the qualified cathode copper of volume production, be its main drawback.
Control cathode potential method, according to the electromotive force of the concentration control cathode of the decopper(ing) arsenic liquid of different steps, control the technic index of product, this kind of method has good control to the hydrogen arsenide of decopper(ing) generation in latter stage, the efficiency of dearsenification is also higher, but because its process characteristic requires flow, electric current is controlled accurately, and require liquid cupric lower (22～15g/L) after the decopper(ing) of one section of electrodeposition, this just makes the efficiency of decopper(ing) not high, and production standard copper under the condition of the low copper of peracid, limited the raising of current density, thereby the throughput of system is difficult to effectively be brought into play.
Can realize electrolytic deposition process production standard copper by high current density, big cycle volume for one section of eddy flow electrodeposition method, and site environment level is better.But this technological equipment investment is large, the more traditional electrodeposition of bath voltage and power consumption is high, and product is that tubular also needs further shaping packing to process, and integrated artistic flow process is complicated, also very limited in industrial application at present.
Summary of the invention
The technical problem to be solved in the present invention is that existing electrodeposition method for decoppering decopper(ing) efficiency is low, cost is higher, can not the high-quality cathode copper of volume production, provide a kind of technique simple for this reason, the cleaning copper electrolyte electrodeposition method for decoppering easy to operate, effect significantly, cost energy consumption is low.
Technical scheme of the present invention is: by Controlling System internal circulating load and Recycle design, current density, to eliminate electrolytic deposition process concentration polarization, realize and produce efficient, the high-quality cathode copper of low cost production, it comprises the following steps:
(1), copper sulfate mother liquor, electrolytic solution and contained waste liquid are stored in and in intercepting basin, form liquid before decopper(ing), composition and index are: containing Cu be 20～70g/L, containing H
2sO
4be 100～300 g/L, 20 ℃～70 ℃ of temperature;
(2) by flow, be, Q
mend decopper(ing) before liquid by intercepting basin, be delivered to Lower tank, it is mixed at Lower tank with electrodeposition circulation fluid, the control indexes of electrodeposition circulation fluid is being 25～55g/L containing Cu, H
2sO
4for 120g～220/L, Q wherein
mend(m
3/ h) can pass through following formula calculative determination:
In formula, M represents the copper molar mass of metal;
Z represents metal ion charge number;
F is Faraday's number 1F=26.8Ah;
I represents system power intensity; N represents electrolyzer quantity;
η represents the energising efficiency of electric current;
C
mend represent the copper ion concentration in the front liquid of decopper(ing);
C
circulation represent the copper ion concentration in electrodeposition circulation fluid
(3), will complete before premixed decopper(ing) liquid and electrodeposition circulation fluid and after plate-type heat exchanger heating, control temperature and be 30 ℃～70 ℃ and send into header tank, by header tank, be dispensed to each copper liberation cell and carry out one section of electrodeposition decopper(ing);
(4), after the decopper(ing) after one section of electrodeposition decopper(ing), liquid is recycled to one section of Lower tank, another part Q by the liquid returning tube part being communicated with each copper liberation cell
go out after the decopper(ing) of flow, liquid is delivered to next process, wherein Q
go out =q
mend .
Before decopper(ing) described in such scheme, in liquid, the current density of electrodeposition decopper(ing) is controlled at 100～400 A/m
2, conduction time, utilization ratio > 95%, and current efficiency > 90%, and the electrodeposition circulation fluid circular flow that enters each copper liberation cell is 10～200 L/min.
The invention has the beneficial effects as follows in original technology and equipment configuration, by less transformation, realize the target of the high-quality cathode copper of output; Saved because producing low-quality cathode copper and returned a series of tooling costs that smelting system brings; Technique is simple, easy to operate, and equipment investment is few; Reduced the dissolving of the anode surface etch resistant layer bringing because of power-off, the life-span of insoluble anode is effectively improved, and greatly reduces the cost of electrolytic deposition process; Reduce to greatest extent the concentration polarization in electrolytic deposition process, make the current density that system held is high, improved the processing power of system.
Accompanying drawing explanation
Fig. 1 is device connection diagram of the present invention.
Embodiment
Below in conjunction with drawings and Examples, the present invention will be further described.
As shown in Figure 1, embodiment 1:
(1), copper sulfate mother liquor, electrolytic solution and contained waste liquid are stored in and in intercepting basin, form liquid before decopper(ing), before decopper(ing), the temperature of liquid is 30 ℃, containing Cu, is 35.2g/L, containing H
2sO
4for 110g/L;
(2) by flow, be, Q
mend =34.1 m
3before the decopper(ing) of/h, liquid is delivered to Lower tank by intercepting basin, makes itself and electrodeposition circulation fluid complete pre-mixing at Lower tank, and making electrodeposition circulation fluid temperature is 35.7 ℃, and Cu content is 30.5g/L, H
2sO
4be 120 g/L;
(3), will complete the front liquid of premixed decopper(ing) and electrodeposition circulation fluid and send into header tank after plate-type heat exchanger heating, circular flow when electrodeposition circulation fluid flows into each copper liberation cell is at 12.4L/min, by header tank, be dispensed to each copper liberation cell and carry out one section of electrodeposition decopper(ing), the current density of one section of electrodeposition decopper(ing) is controlled at 100.3 A/m
2, conduction time, utilization ratio 96.6%;
(4), after the decopper(ing) after one section of electrodeposition decopper(ing), liquid is recycled to one section of Lower tank, another part Q by the liquid returning tube part being communicated with each copper liberation cell
go out =Q
mend =34.1 m
3after the decopper(ing) of/h flow, liquid is delivered to next process.
Embodiment 2:
(1), copper sulfate mother liquor, electrolytic solution and contained waste liquid are stored in and in intercepting basin, form liquid before decopper(ing), before decopper(ing), the temperature of liquid is 60 ℃, containing Cu, is 64.7g/L, containing H
2sO
4for 283g/L;
(2) by flow, be, Q
mend =8.6m
3before the decopper(ing) of/h, liquid is delivered to Lower tank by intercepting basin, makes itself and electrodeposition circulation fluid complete pre-mixing at Lower tank, and making electrodeposition circulation fluid temperature is 45 ℃, and Cu content is 44.9 g/L, H
2sO
4be 120 g/L;
(3) will complete the front liquid of premixed decopper(ing) and electrodeposition circulation fluid and send into header tank after plate-type heat exchanger heating, circular flow when electrodeposition circulation fluid flows into each copper liberation cell is at 175.6L/min, by header tank, be dispensed to each copper liberation cell and carry out one section of electrodeposition decopper(ing), the current density of one section of electrodeposition decopper(ing) is controlled at 352 A/m
2, conduction time, utilization ratio 97%;
(4), after the decopper(ing) after one section of electrodeposition decopper(ing), liquid is recycled to one section of Lower tank, another part Q by the liquid returning tube part being communicated with each copper liberation cell
go out =Q
mend =8.6m
3after the decopper(ing) of/h flow, liquid is delivered to next process.
Embodiment 3:(1), copper sulfate mother liquor, electrolytic solution and contained waste liquid are stored in and in intercepting basin, form liquid before decopper(ing), before decopper(ing), the temperature of liquid is 20 ℃, containing Cu, is 20g/L, containing H
2sO
4for 100g/L;
(2) by flow, be, Q
mend =34.1 m
3before the decopper(ing) of/h, liquid is delivered to Lower tank by intercepting basin, makes itself and electrodeposition circulation fluid complete pre-mixing at Lower tank, and making electrodeposition circulation fluid temperature is 35.7 ℃, and Cu content is 25g/L, H
2sO
4be 120 g/L.
(3), will complete the front liquid of premixed decopper(ing) and electrodeposition circulation fluid and send into header tank after plate-type heat exchanger heating, circular flow when electrodeposition circulation fluid flows into each copper liberation cell is at 10L/min, by header tank, be dispensed to each copper liberation cell and carry out one section of electrodeposition decopper(ing), the current density of one section of electrodeposition decopper(ing) is controlled at 100 A/m
2, conduction time, utilization ratio 96%;
(4), after the decopper(ing) after one section of electrodeposition decopper(ing), liquid is recycled to one section of Lower tank, another part Q by the liquid returning tube part being communicated with each copper liberation cell
go out =Q
mend =34.1 m
3after the decopper(ing) of/h flow, liquid is delivered to next process.
Embodiment 4:(1), copper sulfate mother liquor, electrolytic solution and contained waste liquid are stored in and in intercepting basin, form liquid before decopper(ing), before decopper(ing), the temperature of liquid is 70 ℃, containing Cu, is 70g/L, containing H
2sO
4for 300g/L;
(2) by flow, be, Q
mend =34.1 m
3before the decopper(ing) of/h, liquid is delivered to Lower tank by intercepting basin, makes itself and electrodeposition circulation fluid complete pre-mixing at Lower tank, and making electrodeposition circulation fluid temperature is 35.7 ℃, and Cu content is 55g/L, H
2sO
4be 220 g/L.
(3), will complete the front liquid of premixed decopper(ing) and electrodeposition circulation fluid and send into header tank after plate-type heat exchanger heating, circular flow when electrodeposition circulation fluid flows into each copper liberation cell is at 10L/min, by header tank, be dispensed to each copper liberation cell and carry out one section of electrodeposition decopper(ing), the current density of one section of electrodeposition decopper(ing) is controlled at 400 A/m
2, conduction time, utilization ratio 96%;
(4), after the decopper(ing) after one section of electrodeposition decopper(ing), liquid is recycled to one section of Lower tank, another part Q by the liquid returning tube part being communicated with each copper liberation cell
go out =Q
mend =34.1 m
3after the decopper(ing) of/h flow, liquid is delivered to next process.
The preferred embodiments of the present invention 5:
(1), copper sulfate mother liquor, electrolytic solution and contained waste liquid are stored in and in intercepting basin, form liquid before decopper(ing), before decopper(ing), the temperature of liquid is 58 ℃, containing Cu, is 49.5g/L, containing H
2sO
4for 162g/L;
(2) by flow, be, Q
mend =19.8m
3before the decopper(ing) of/h, liquid is delivered to Lower tank by intercepting basin, makes itself and electrodeposition circulation fluid complete pre-mixing at Lower tank, and making electrodeposition circulation fluid temperature is 40.2 ℃, and Cu content is 40.9g/L, H
2sO
4be 120 g/L.
(3) will complete the front liquid of premixed decopper(ing) and electrodeposition circulation fluid and send into header tank after plate-type heat exchanger heating, circular flow when electrodeposition circulation fluid flows into each copper liberation cell is at 158.6 L/min, by header tank, be dispensed to each copper liberation cell and carry out one section of electrodeposition decopper(ing), the current density of one section of electrodeposition decopper(ing) is controlled at 266 A/m
2, conduction time, utilization ratio 96%;
(4), after the decopper(ing) after one section of electrodeposition decopper(ing), liquid is recycled to one section of Lower tank, another part Q by the liquid returning tube part being communicated with each copper liberation cell
go out =Q
mend =19.8 m
3after the decopper(ing) of/h flow, liquid is delivered to next process.
The index that records cathode copper is as follows:
| Element | Cu | Se | Te | Bi | Cr | Mn |
| Content | 99.97826 | 0.00001 | 0.00007 | 0.00033 | 0.00001 | 0.00001 |
| Sb | Cd | As | P | Pb | S | Sn |
| 0.00027 | 0.00001 | 0.00089 | 0.00001 | 0.00059 | 0.01591 | 0.00001 |
| Ni | Fe | Si | Zn | Co | Ag | |
| 0.00299 | 0.00005 | 0.00005 | 0.00004 | 0.00002 | 0.00046 |
The preferred embodiments of the present invention 6:
(1), copper sulfate mother liquor, electrolytic solution and contained waste liquid are stored in and in intercepting basin, form liquid before decopper(ing), before decopper(ing), the temperature of liquid is 55 ℃, containing Cu, is 52.5g/L, containing H
2sO
4for 196g/L;
(2) by flow, be, Q
mend =7.8 m
3before the decopper(ing) of/h, liquid is delivered to Lower tank by intercepting basin, makes itself and electrodeposition circulation fluid complete pre-mixing at Lower tank, and making electrodeposition circulation fluid temperature is 45.5 ℃, and Cu content is 35.1g/L, H
2sO
4be 120 g/L.
(3) will complete the front liquid of premixed decopper(ing) and electrodeposition circulation fluid and send into header tank after plate-type heat exchanger heating, circular flow when electrodeposition circulation fluid flows into each copper liberation cell is at 158.6 L/min, by header tank, be dispensed to each copper liberation cell and carry out one section of electrodeposition decopper(ing), the current density of one section of electrodeposition decopper(ing) is controlled at 200 A/m
2, conduction time, utilization ratio 96%;
(4) after the decopper(ing), after one section of electrodeposition decopper(ing), liquid is recycled to one section of Lower tank by the liquid returning tube part being communicated with each copper liberation cell, and after the decopper(ing) of another part Q1 flow, liquid is delivered to next process.
The index that records cathode copper is as follows:
| Element | Cu | Se | Te | Bi | Cr | Mn |
| Content | 99.99593 | 0.00001 | 0.00003 | 0.00001 | 0.00003 | 0.00001 |
| Sb | Cd | As | P | Pb | S | Sn |
| 0.00001 | 0.00001 | 0.00075 | 0.00001 | 0.00073 | 0.00161 | 0.00007 |
| Ni | Fe | Si | Zn | Co | Ag | ? |
| 0.00013 | 0.00001 | 0.00052 | 0.00001 | 0.00002 | 0.00055 | ? |
By reference to the accompanying drawings the present invention is exemplarily described above; obviously specific implementation of the present invention is not subject to the restrictions described above; as long as adopted the improvement of the various unsubstantialities that method of the present invention design and technical scheme carry out; or without improving, design of the present invention and technical scheme are directly applied to other occasion, all within protection scope of the present invention.
Claims (2)
1. a method for the high-quality cathode copper of cleaning copper electrolyte process High-efficient Production, is characterized in that it comprises the following steps:
(1), copper sulfate mother liquor, electrolytic solution and contained waste liquid are stored in and in intercepting basin, form liquid before decopper(ing), composition and index are: containing Cu be 20～70g/L, containing H
2sO
4be 100～300 g/L, 20 ℃～70 ℃ of temperature;
(2) by flow, be, Q
mend decopper(ing) before liquid by intercepting basin, be delivered to Lower tank, it is mixed at Lower tank with electrodeposition circulation fluid, the control indexes of electrodeposition circulation fluid is being 25～55g/L containing Cu, H
2sO
4for 120g～220/L;
(3) will complete before premixed decopper(ing) liquid and electrodeposition circulation fluid and after plate-type heat exchanger heating, control temperature and be 30 ℃～70 ℃ and send into header tank, and by header tank, be dispensed to each copper liberation cell and carry out one section of electrodeposition decopper(ing);
(4), after the decopper(ing) after one section of electrodeposition decopper(ing), liquid is recycled to one section of Lower tank, another part Q by the liquid returning tube part being communicated with each copper liberation cell
go out after the decopper(ing) of flow, liquid is delivered to next process, wherein Q
go out =q
mend .
2. the high electrodeposition method for decoppering of decopper(ing) efficiency as claimed in claim 1, the current density that it is characterized in that described one section of electrodeposition decopper(ing) is controlled at 100～400 A/m2, conduction time, utilization ratio > 95%, current efficiency > 90%, and the electrodeposition circulation fluid circular flow that enters each copper liberation cell is 10～200 L/min.
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|---|---|---|---|
| CN201310462351.XA CN103526230B (en) | 2013-10-08 | 2013-10-08 | A kind of method of cleaning copper electrolyte processing efficient production high-quality cathode copper |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104894607A (en) * | 2015-05-22 | 2015-09-09 | 铜陵有色设计研究院 | Method for purifying waste copper sulfate electrolyte |
| CN108546963A (en) * | 2018-05-31 | 2018-09-18 | 西北矿冶研究院 | Method for improving purification efficiency of copper electrolyte |
| CN110219018A (en) * | 2019-05-28 | 2019-09-10 | 西北矿冶研究院 | Device and method for industrially implementing magnetized copper electrolysis |
| CN111254463A (en) * | 2020-03-10 | 2020-06-09 | 吉林紫金铜业有限公司 | Decoppering system |
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| JPS5620185A (en) * | 1979-07-25 | 1981-02-25 | Nippon Mining Co Ltd | Copper and arsenic removing method for copper electrolyte |
| JPS6050192A (en) * | 1983-08-27 | 1985-03-19 | Unitika Ltd | Purifying method of copper electrolyte |
| JPS62284025A (en) * | 1986-06-03 | 1987-12-09 | Mitsubishi Metal Corp | Method for recovering refined nickel sulfate from copper electrolyte |
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2013
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| JPS5620185A (en) * | 1979-07-25 | 1981-02-25 | Nippon Mining Co Ltd | Copper and arsenic removing method for copper electrolyte |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104894607A (en) * | 2015-05-22 | 2015-09-09 | 铜陵有色设计研究院 | Method for purifying waste copper sulfate electrolyte |
| CN108546963A (en) * | 2018-05-31 | 2018-09-18 | 西北矿冶研究院 | Method for improving purification efficiency of copper electrolyte |
| CN110219018A (en) * | 2019-05-28 | 2019-09-10 | 西北矿冶研究院 | Device and method for industrially implementing magnetized copper electrolysis |
| CN111254463A (en) * | 2020-03-10 | 2020-06-09 | 吉林紫金铜业有限公司 | Decoppering system |
| CN111254463B (en) * | 2020-03-10 | 2021-05-04 | 吉林紫金铜业有限公司 | Decoppering system |
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|---|---|
| CN103526230B (en) | 2015-12-09 |
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Effective date of registration: 20190726 Address after: 244000 West Building of Changjiang West Road Nonferrous Courtyard, Tongling City, Anhui Province Patentee after: Tongling Nonferrous Metals Group Co., Ltd. Address before: 244000 Meitang New Village, Tongling County, Tongling City, Anhui Province Patentee before: Tongling Nonferrous Metal Group Co., Ltd's Jinchang Smelter |
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