CN103526230B - A kind of method of cleaning copper electrolyte processing efficient production high-quality cathode copper - Google Patents

A kind of method of cleaning copper electrolyte processing efficient production high-quality cathode copper Download PDF

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CN103526230B
CN103526230B CN201310462351.XA CN201310462351A CN103526230B CN 103526230 B CN103526230 B CN 103526230B CN 201310462351 A CN201310462351 A CN 201310462351A CN 103526230 B CN103526230 B CN 103526230B
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ing
decopper
liquid
electrodeposition
copper
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CN103526230A (en
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吕高平
赵荣升
张志国
孙成明
朱芳宝
唐文忠
沈煜
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Tongling Nonferrous Metals Group Co Ltd
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Tongling Nonferrous Metal Group Co Ltd's Jinchang Smelter
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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
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Abstract

The invention discloses a kind of method of cleaning copper electrolyte processing efficient production high-quality cathode copper, it comprises: (1), copper sulfate mother liquor, electrolytic solution and contained waste liquid to be stored in intercepting basin and to form liquid before decopper(ing); (2) be, Q<b><iGreatT.Gre aT.GT by flow mendbefore the decopper(ing) of </i></bGreatT.Gr eaT.GT, liquid is delivered to Lower tank by intercepting basin, makes it mix at Lower tank with electrodeposition circulation fluid; (3) by complete pre-mixing decopper(ing) before liquid and electrodeposition circulation fluid control temperature after plate-type heat exchanger heating be 30 DEG C ~ 70 DEG C feeding header tanks, be dispensed to each copper liberation cell by header tank 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 by the liquid returning tube part that is communicated with each copper liberation cell, another part Q<b><iGreatT.Gre aT.GT go outafter the decopper(ing) of </i></bGreatT.Gr eaT.GT flow, liquid is delivered to next process, wherein Q<i> go out</i><iGreatT.Gre aT.GT=</i>Q<iGre atT.GreaT.GT mend</i>.By less transformation, realize the target of output high-quality cathode copper.

Description

A kind of method of cleaning copper electrolyte processing efficient production high-quality cathode copper
Technical field
The present invention relates to the electro-deposition techniques of copper metal in hydrometallurgy process solution, especially in cleaning copper electrolyte dedoping step, remove the method for copper in electrolytic solution.
Background technology
In existing cleaning copper electrolyte impurity removing technology, industrial most widely used be still utilize insoluble anode electrodeposition method to remove copper and arsenic, antimony, bismuth etc. in electrolytic solution, through years of researches and improvement, have developed multiple electrodeposition method for decoppering: be interrupted electrodeposition method, continuously electrodeposition method (namely inducing dearsenification method), limit current density method, control cathode potential method, eddy flow electrodeposition method;
The rate of recovery that these methods mainly produce latter stage such as antimony, bismuth, nickel etc. in arsine gas deterioration production environment and raising electrolytic solution for electrodeposition decopper(ing) has more research.But it is relatively less for the research improving cathode copper quality product in purification decopper(ing) process.
Be interrupted electrodeposition method, also referred to as one section of decopper(ing) method, commonly use in some middle-size and small-size factories.This method is put in a cell by the solution of cupric and impurity, disposable by its electrodeposition to copper, degree that arsenic concentration is lower.In the electrodeposition later stage, arsenic, antimony, bismuth and copper separate out at negative electrode the smelting system that the high copper sponge of the impurity that produces returns pyrogenic process, cause the vicious cycle in the entire system of the impurity such as arsenic on the one hand, add processing cost on the other hand.
Continuous decopper(ing) dearsenification electrodeposition method, also referred to as revulsion dearsenification.Within 1980, invented, introduced China with 1985 by SUMITOMO CHEMICAL metal mine Co., Ltd., application and the purification system of more domestic large-scale cupric electrolysis factories, obtained good effect.Revulsion is mainly through supplementary assisted solution, and maintenance copper, arsonium ion realize the maximum removal efficiency of arsenic in certain concentration range, and control the generation of arsine gas.This method more pays attention to removing of arsenic, though tabular electrolytic copper can be produced in front several copper liberation cell, usually by the constraint of whole system processing condition, tabular electrolytic copper also often impure element is higher and directly return smelting system.
Limit current density method, this kind of method has good control to the hydrogen arsenide that decopper(ing) produces latter stage, and the efficiency of dearsenification is also higher, but current density is less, and can not volume production acceptable cathodic copper, is its main drawback.
Control cathode potential method, the technic index of product is controlled according to the electromotive force of the concentration control cathode of the decopper(ing) arsenic liquid of different steps, the hydrogen arsenide of this kind of method to decopper(ing) generation in latter stage has good control, the efficiency of dearsenification is also higher, but because its process characteristic requires flow, electric current controls accurately, and liquid cupric lower (22 ~ 15g/L) after requiring 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, limit the raising of current density, thus the throughput of system is difficult to effectively be played.
One section of eddy flow electrodeposition method can realize electrolytic deposition process production standard copper by high current density, big cycle volume, and site environment level is better.But this technological equipment investment is large, bath voltage is high with the more traditional electrodeposition of power consumption, and product is that tubular also needs further shaping to pack process, and integrated artistic flow process complexity, industrially applies also very limited 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 volume production high-quality cathode copper, there is provided a kind of technique simple for this reason, easy to operate, the cleaning copper electrolyte electrodeposition method for decoppering that Be very effective, cost energy consumption are low.
Technical scheme of the present invention is: by Controlling System internal circulating load and Recycle design, current density, and to eliminate electrolytic deposition process concentration polarization, realize producing efficient, low cost production high-quality cathode copper, it comprises the following steps:
(1), by copper sulfate mother liquor, electrolytic solution and contained waste liquid be stored in intercepting basin and form liquid before decopper(ing), composition and index are: containing Cu be 20 ~ 70g/L, containing H 2sO 4be 100 ~ 300g/L, temperature 20 DEG C ~ 70 DEG C;
(2) be, Q by flow mend decopper(ing) before liquid be delivered to Lower tank by intercepting basin, make it mix at Lower tank with electrodeposition circulation fluid, the control indexes of electrodeposition circulation fluid is being 25 ~ 55g/L, H containing Cu 2sO 4for 120g ~ 220/L, wherein Q mend(m 3/ h) determine by following formula calculating:
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 copper ion concentration before expression decopper(ing) in liquid;
C circulation represent the copper ion concentration in electrodeposition circulation fluid
(3), by complete pre-mixing decopper(ing) before liquid and electrodeposition circulation fluid control temperature after plate-type heat exchanger heating be 30 DEG C ~ 70 DEG C feeding header tanks, be dispensed to each copper liberation cell by header tank 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 by the liquid returning tube part that is communicated with each copper liberation cell, another part Q 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) controls at 100 ~ 400A/m 2, conduction time utilization ratio > 95%, current efficiency > 90%, the electrodeposition circulation fluid circular flow entering each copper liberation cell is 10 ~ 200L/min.
The invention has the beneficial effects as follows in original technology and equipment configuration, by less transformation, realize the target of output high-quality cathode copper; The a series of tooling costs brought because producing low-quality cathode copper melt back refining system are saved; Technique is simple, and easy to operate, equipment investment is few; Decrease the dissolving of the anode surface etch resistant layer brought because of power-off, the life-span of insoluble anode is effectively improved, and greatly reduces the cost of electrolytic deposition process; Reduce the concentration polarization in electrolytic deposition process to greatest extent, make the current density that system held is high, improve 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), by copper sulfate mother liquor, electrolytic solution and contained waste liquid be stored in intercepting basin and form liquid before decopper(ing), before decopper(ing), the temperature of liquid is 30 DEG C, is 35.2g/L, containing H containing Cu 2sO 4for 110g/L;
(2) be, Q by flow mend =34.1m 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 make electrodeposition circulation fluid temperature be 35.7 DEG C, Cu content is 30.5g/L, H 2sO 4for 120g/L;
(3), liquid before the decopper(ing) completing pre-mixing and electrodeposition circulation fluid are sent 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, be dispensed to each copper liberation cell by header tank and carry out one section of electrodeposition decopper(ing), the current density of one section of electrodeposition decopper(ing) controls at 100.3A/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 by the liquid returning tube part that is communicated with each copper liberation cell, another part Q go out =Q mend =34.1m 3after the decopper(ing) of/h flow, liquid is delivered to next process.
Embodiment 2:
(1), by copper sulfate mother liquor, electrolytic solution and contained waste liquid be stored in intercepting basin and form liquid before decopper(ing), before decopper(ing), the temperature of liquid is 60 DEG C, is 64.7g/L, containing H containing Cu 2sO 4for 283g/L;
(2) be, Q by flow 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 make electrodeposition circulation fluid temperature be 45 DEG C, Cu content is 44.9g/L, H 2sO 4for 120g/L;
(3) liquid before the decopper(ing) completing pre-mixing and electrodeposition circulation fluid are sent 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, be dispensed to each copper liberation cell by header tank and carry out one section of electrodeposition decopper(ing), the current density of one section of electrodeposition decopper(ing) controls at 352A/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 by the liquid returning tube part that is communicated with each copper liberation cell, another part Q 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 be stored in intercepting basin form liquid before decopper(ing), before decopper(ing), the temperature of liquid is 20 DEG C, is 20g/L, containing H containing Cu 2sO 4for 100g/L;
(2) be, Q by flow mend =34.1m 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 make electrodeposition circulation fluid temperature be 35.7 DEG C, Cu content is 25g/L, H 2sO 4for 120g/L.
(3), liquid before the decopper(ing) completing pre-mixing and electrodeposition circulation fluid are sent 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, be dispensed to each copper liberation cell by header tank and carry out one section of electrodeposition decopper(ing), the current density of one section of electrodeposition decopper(ing) controls at 100A/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 that is communicated with each copper liberation cell, another part Q go out =Q mend =34.1m 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 be stored in intercepting basin form liquid before decopper(ing), before decopper(ing), the temperature of liquid is 70 DEG C, is 70g/L, containing H containing Cu 2sO 4for 300g/L;
(2) be, Q by flow mend =34.1m 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 make electrodeposition circulation fluid temperature be 35.7 DEG C, Cu content is 55g/L, H 2sO 4for 220g/L.
(3), liquid before the decopper(ing) completing pre-mixing and electrodeposition circulation fluid are sent 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, be dispensed to each copper liberation cell by header tank and carry out one section of electrodeposition decopper(ing), the current density of one section of electrodeposition decopper(ing) controls at 400A/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 that is communicated with each copper liberation cell, another part Q go out =Q mend =34.1m 3after the decopper(ing) of/h flow, liquid is delivered to next process.
The preferred embodiments of the present invention 5:
(1), by copper sulfate mother liquor, electrolytic solution and contained waste liquid be stored in intercepting basin and form liquid before decopper(ing), before decopper(ing), the temperature of liquid is 58 DEG C, is 49.5g/L, containing H containing Cu 2sO 4for 162g/L;
(2) be, Q by flow 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 make electrodeposition circulation fluid temperature be 40.2 DEG C, Cu content is 40.9g/L, H 2sO 4for 120g/L.
(3) liquid before the decopper(ing) completing pre-mixing and electrodeposition circulation fluid are sent into header tank after plate-type heat exchanger heating, circular flow when electrodeposition circulation fluid flows into each copper liberation cell is at 158.6L/min, be dispensed to each copper liberation cell by header tank and carry out one section of electrodeposition decopper(ing), the current density of one section of electrodeposition decopper(ing) controls at 266A/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 that is communicated with each copper liberation cell, another part Q go out =Q mend =19.8m 3after the decopper(ing) of/h flow, liquid is delivered to next process.
The index recording 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), by copper sulfate mother liquor, electrolytic solution and contained waste liquid be stored in intercepting basin and form liquid before decopper(ing), before decopper(ing), the temperature of liquid is 55 DEG C, is 52.5g/L, containing H containing Cu 2sO 4for 196g/L;
(2) be, Q by flow mend =7.8m 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 make electrodeposition circulation fluid temperature be 45.5 DEG C, Cu content is 35.1g/L, H 2sO 4for 120g/L.
(3) liquid before the decopper(ing) completing pre-mixing and electrodeposition circulation fluid are sent into header tank after plate-type heat exchanger heating, circular flow when electrodeposition circulation fluid flows into each copper liberation cell is at 158.6L/min, be dispensed to each copper liberation cell by header tank and carry out one section of electrodeposition decopper(ing), the current density of one section of electrodeposition decopper(ing) controls at 200A/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 that is communicated with each copper liberation cell, and after the decopper(ing) of another part Q1 flow, liquid is delivered to next process.
The index recording 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
Above by reference to the accompanying drawings to invention has been exemplary description; obvious specific implementation of the present invention is not subject to the restrictions described above; as long as have employed the improvement of the various unsubstantialities that method of the present invention is conceived and technical scheme is carried out; or design of the present invention and technical scheme directly applied to other occasion, all within protection scope of the present invention without to improve.

Claims (2)

1. a method for cleaning copper electrolyte processing efficient production high-quality cathode copper, is characterized in that it comprises the following steps:
(1), by copper sulfate mother liquor, electrolytic solution and contained waste liquid be stored in intercepting basin and form liquid before decopper(ing), composition and index are: containing Cu be 20 ~ 70g/L, containing H 2sO 4be 100 ~ 300g/L, temperature 20 DEG C ~ 70 DEG C;
(2) be, Q by flow mend decopper(ing) before liquid be delivered to Lower tank by intercepting basin, make it mix at Lower tank with electrodeposition circulation fluid, the control indexes of electrodeposition circulation fluid is being 25 ~ 55g/L, H containing Cu 2sO 4be 120 ~ 220g/L;
(3) by complete pre-mixing decopper(ing) before liquid and electrodeposition circulation fluid control temperature after plate-type heat exchanger heating be 30 DEG C ~ 70 DEG C feeding header tanks, be dispensed to each copper liberation cell by header tank 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 by the liquid returning tube part that is communicated with each copper liberation cell, another part Q go out after the decopper(ing) of flow, liquid is delivered to next process, wherein Q go out =q mend .
2. the electrodeposition method for decoppering that decopper(ing) efficiency as claimed in claim 1 is high, is characterized in that the current density of described one section of electrodeposition decopper(ing) controls at 100 ~ 400A/m 2, conduction time utilization ratio > 95%, current efficiency > 90%, the electrodeposition circulation fluid circular flow entering each copper liberation cell is 10 ~ 200L/min.
CN201310462351.XA 2013-10-08 2013-10-08 A kind of method of cleaning copper electrolyte processing efficient production high-quality cathode copper Active CN103526230B (en)

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CN104894607A (en) * 2015-05-22 2015-09-09 铜陵有色设计研究院 Method for purifying waste copper sulfate electrolyte
CN108546963B (en) * 2018-05-31 2020-05-22 西北矿冶研究院 Method for improving purification efficiency of copper electrolyte
CN110219018B (en) * 2019-05-28 2021-04-16 西北矿冶研究院 Device and method for industrially implementing magnetized copper electrolysis
CN111254463B (en) * 2020-03-10 2021-05-04 吉林紫金铜业有限公司 Decoppering system

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