CN1309849C - Method of dearsenic by parallel circulating continuous electric formation - Google Patents
Method of dearsenic by parallel circulating continuous electric formation Download PDFInfo
- Publication number
- CN1309849C CN1309849C CNB200410021941XA CN200410021941A CN1309849C CN 1309849 C CN1309849 C CN 1309849C CN B200410021941X A CNB200410021941X A CN B200410021941XA CN 200410021941 A CN200410021941 A CN 200410021941A CN 1309849 C CN1309849 C CN 1309849C
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- Prior art keywords
- dearsenification
- solution
- copper
- electrodeposition
- circulation
- Prior art date
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- Expired - Lifetime
Links
- 238000000034 method Methods 0.000 title claims abstract description 49
- 230000015572 biosynthetic process Effects 0.000 title claims description 3
- 239000010949 copper Substances 0.000 claims abstract description 52
- 239000000243 solution Substances 0.000 claims abstract description 29
- 229910052785 arsenic Inorganic materials 0.000 claims abstract description 26
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 16
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052802 copper Inorganic materials 0.000 claims abstract description 16
- 239000008151 electrolyte solution Substances 0.000 claims abstract description 9
- 229910000563 Arsenical copper Inorganic materials 0.000 claims abstract description 3
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910001431 copper ion Inorganic materials 0.000 claims abstract 2
- 238000004070 electrodeposition Methods 0.000 claims description 33
- 239000007788 liquid Substances 0.000 claims description 20
- 239000012530 fluid Substances 0.000 claims description 11
- JEMGLEPMXOIVNS-UHFFFAOYSA-N arsenic copper Chemical compound [Cu].[As] JEMGLEPMXOIVNS-UHFFFAOYSA-N 0.000 claims description 8
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 4
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 239000012452 mother liquor Substances 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 2
- 238000001802 infusion Methods 0.000 claims description 2
- 239000002659 electrodeposit Substances 0.000 abstract 3
- 239000000203 mixture Substances 0.000 description 15
- 239000002893 slag Substances 0.000 description 10
- 238000005516 engineering process Methods 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 4
- 229910000070 arsenic hydride Inorganic materials 0.000 description 3
- 230000000737 periodic effect Effects 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 101100433727 Caenorhabditis elegans got-1.2 gene Proteins 0.000 description 1
- 241000080590 Niso Species 0.000 description 1
- 230000004308 accommodation Effects 0.000 description 1
- RBFQJDQYXXHULB-UHFFFAOYSA-N arsane Chemical compound [AsH3] RBFQJDQYXXHULB-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000009854 hydrometallurgy Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000011236 particulate material Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000010079 rubber tapping Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Images
Classifications
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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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- Electrolytic Production Of Metals (AREA)
Abstract
The present invention relates to a method of dearsenic by parallel circulating continuous electro deposit. An electrolytic solution flows in an electro deposit dearsenization slot as a parallel connection circulation form, the circulation solution is heated, the temperature is controlled at 60 to 66 DEG C, and the solution is completely supplied in electro deposit dearsenization processes. The flow rate of the supply solution is equal to that of discharge liquor and is controlled as 1 to 20m<3>/h, and the ratio of Cu to As in the supply solution is 1.5 to 3: 1 to 1.5. A part of electrolyzer is used as an end point slot, copper ion Cu<2+> concentration in discharge solution of the end point slot is controlled as 0.5 to 2.5 g/L, the dearsenization supply solution , the circulation solution and the end point discharge solution are controlled so as to form arsenical copper Cu2As and Cu3As via arsenic and copper in the process of dearsenization, and Cu2As is prepared as much as possible.
Description
Technical field
The present invention relates to remove in the hydrometallurgy process technology of arsenic in the solution, the parallel connection that especially in copper electrolytic process, removes arsenic in its electrolytic solution continuous electrodeposition dearsenification method that circulates.
Background technology
Electrodeposition dearsenification method is adopted in the purification dearsenification of electrolytic solution in cupric electrolysis is produced, the overwhelming majority.Mainly contain following several method: extremely take off method, two sections dearsenification methods, periodic reverse current electrodeposition dearsenification method, limit current density electrodeposition dearsenification methods, induce dearsenification method, control cathode electromotive force electrodeposition dearsenification method etc.
Preceding two kinds of arsenic removing methods exist dearsenification efficient low, how below 50%; And be accompanied by a large amount of AsH
3Severe toxicity gas produces, and power consumption is big, its direct current unit consumption＞33000kw.h/t
AsShortcomings such as (power consumptions that removes that contains copper in the dearsenification process).
The four kinds of arsenic removing methods in back reduce and inhibition AsH at the decreasing ratio that improves arsenic
3Aspects such as the generation of gas have obtained achievement preferably.But these methods all exist current density low; The energy consumption height, its direct current unit consumption＞25000kw.h/t
As(power consumption that removes that contains copper in the dearsenification process); AsH
3Shortcoming such as still produce latter stage in dearsenification.Therefore, even under the situation that its dearsenification efficient improves, its equipment capacity also is very low.
In addition, in whole flow process, exist a large amount of copper to be disabled and remove, and enter various flow process materials, as black copper plate, arsenic slag etc.This has just increased the loss of copper in overall flow; And increased the power consumption that is used for decopper(ing), and increase the dearsenification cost.
And these methods are to be based upon on the use of specific installation and the configuration of special equipment.As periodic reverse current electrodeposition dearsenification method, adopt the silicon rectifier of energy periodic reverse.Limit current density electrodeposition dearsenification method adopts the computer control silicon-controlled rectifier that electric current is accurately controlled.Both require the back solution flow, electric current are accurately controlled, and its electrolyzer adopts special stagger to realize the series flow of solution between electrolyzer.Therefore, their equipment input is very big; And at solution flow, the isoparametric control precision prescribed of size of current height, the control difficulty.
Summary of the invention
Deficiency at above-mentioned prior art existence, the present invention proposes the continuous electrodeposition dearsenification method of a kind of circulation in parallel, under the equipment and equipment configuration of original technology, by control of process parameters and adjustment are realized continuous dearsenification, be that a kind of control is simple, operation is succinct, obvious results copper electrolyte electrodeposition arsenic removing method.
The present invention realizes by following technical measures:
1, the control of solution circulated: solution parallel connection between groove circulates; Circulation fluid is heated, and its temperature is controlled at 60～66 ℃.
Electrodeposition dearsenification groove solution is carried out comprehensive fluid infusion.As the terminal point groove, its solution is discharged system, with balanced solution volume and composition with the part electrolyzer.The bulking liquor flow equates with the liquid effluent flow, i.e. Q
2=Q
3The supply liquid measure is proportional to the electric current that the electrodeposition dearsenification is supplied with, generally at 1～20m
3Between/the h.
Behind copper sulfate mother liquor, the decopper(ing) in liquid, the electrolytic solution any one, or the mixed solution between them can make it to be complementary with electric current, solution compolision, electrodeposition dearsenification groove number as the bulking liquor of dearsenification process, and its occurrence formula is calculated as described below determined:
Iqtn＝Q
2C
2-Q
3C
3
In the formula: I---strength of current (KA), I=D
K* A.D
KBe cathode current density, at 195～320A/m
2Between; A is a cathode area, is decided by the area of monolithic negative electrode and the piece number of a groove inner cathode.
Q---electrochemical equivalent (g.A
-1.h
-1), q
As (v)=0.5588g.A
-1.h
-1, q
Cu2+=1.1852g.A
-1.h
-1
T---the time (h), when aforementioned calculation, got 1 hour.N---electrodeposition dearsenification groove number.
Q
2, Q
3---bulking liquor, liquid effluent flow (m
3/ h).Q
2＝Q
3。C
2, C
3---bulking liquor, liquid effluent concentration (g/L).
Bulking liquor copper arsenic ratio is controlled at Cu: As=1.5～3: 1～1.5; Dearsenification terminal point liquid composition: Cu
2+=0.5～2.5g/L.
2, the control of solution parameter:
Liquid copper arsenic ratio is controlled at Cu: As=1.5～3: 1～1.5 before the dearsenification, so that arsenic and copper formation arsenical copper Cu in the dearsenification process
2As, Cu
3As, and generate Cu as far as possible
2As.
3, cathode material: negative electrode adopts complete copper anode or the anode scrap of profile, or other metal block.
Description of drawings
Fig. 1 is a dearsenification schema of the present invention.
Fig. 2 is that equipment and technology connect figure.As liquid, electrolytic solution behind the copper sulfate mother liquor of dearsenification process bulking liquor, the decopper(ing), or the mixed solution between them is introduced into intercepting basin, then with Q
2Amount mend into circulation fluid, make them enter electrodeposition dearsenification groove together, press Q by a part of solution after the electrodeposition dearsenification
3Amount discharge system, deliver to next process; And brother's part solution Q
4Return circulation groove, the circulation rework solution through the steam heating of interchanger, is delivered to header tank by the conveying of pump, and then by the discrepancy in elevation, solution flow to electrodeposition dearsenification groove from header tank and carries out the electrodeposition dearsenification.
1., bulking liquor can be any one in liquid behind copper sulfate mother liquor, the decopper(ing), the electrolytic solution in the dearsenification process, or the mixed solution between them.
2., bulking liquor is mended inbound traffics (Q in the dearsenification process
2) and liquid effluent flow (Q
3) equate.Be Q
2=Q
3
3., Q
1, Q
1Be respectively circulating fluid flow rate and circulation rework solution flow.
4., bulking liquor flow size is decided by dearsenification groove number, dearsenification electric current, bulking liquor composition in the dearsenification process.Its value can be calculated by following equation:
Iqtn＝Q
2C
2-Q
3C
3
5., the circulation fluid in the dearsenification process must heat, and it is maintained between 60～66 ℃.
Bulking liquor is by after the electrodeposition dearsenification, and the arsenic slag of output is delivered to the recycling of postorder operation; And liquid can be produced NiSO and use it for according to the nickeliferous concentration of solution after the dearsenification
47H
2O or directly return electrolytic copper production cycle system.
Advantage of the present invention and good effect:
1, the present invention can under the equipment and equipment configuration of original technology, realize continuous dearsenification. And it is simple to have equipment, and gives birth to Production capacity power is big, drops into little; The dearsenification of applicant's electrodeposition still can not be satisfied 90,000 tons of required taking off of Cu-CATH-1 of production at original 36 grooves The arsenic ability has reached present 24 grooves and just can satisfy the required dearsenification ability of Cu-CATH-1 more than 200,000 tons of producing.
2, can establishment AsH3The ability that produces, and make all Winning cells be in best dearsenification state; Control method is succinct, Be easy to realize; Energy consumption is low; System's solution compolision is even; According to the dearsenification scene is detected, do not measure AsH3 This illustrates this Technology has and extremely effectively suppresses AsH3The ability that produces.
3, the arsenic slag goes out groove easily, and is simple to operate. Make the physical appearance of arsenic slag be controlled to be particulate material by the technology adjustment. Take off groove Through after the production of one-period, solution is wherein discharged, then the arsenic slag in the groove is shoveled out or extracts out, by suction filtration or plate Separation of Solid and Liquid is carried out in the frame press filtration. Therefore, be more convenient for the operation of tapping process.
The copper arsenic ratio of arsenic slag can be controlled in Cu: As=2～3: 1～1.5, even close to minimum theoretical value Cu2The Cu of As: As=1.71: 1. Improved the effective rate of utilization of copper in the electrodeposition dearsenification process, and reduced that invalid copper is a large amount of in the dearsenification process to exist institute to draw The process loss that rises and the consumption of electric energy. Dearsenification direct current consumption≤15000kwh/tAs(the electricity that removes that contains copper in the dearsenification process Consumption).
4, current density height, capacity of equipment are big, and wide accommodation, can be controlled in 195～320A/m2Between.
Embodiment:
Embodiment 1: bulking liquor contains composition: Cu=31.51g/L, As=19.94g/L, Cu: As=1.580: 1.Bulking liquor flow 4.2m
3/ h.63 ℃ of circulation fluid temperature.24 of electrodeposition dearsenification grooves.Dearsenification electric current 10.0KA.Terminal point liquid composition Cu=0.97g/L, As=1.86g/L.Arsenic slag composition Cu=38.40%, As=19.85, copper arsenic is than being Cu: As=1.935: 1.
Embodiment 2: bulking liquor contains composition: Cu=23.37g/L, As=13.18g/L, Cu: As=1.773: 1.Bulking liquor flow 4.2m
3/ h.62 ℃ of circulation fluid temperature.24 of electrodeposition dearsenification grooves.Dearsenification electric current 9.0KA.Terminal point liquid composition Cu=1.48g/L, As=1.39g/L.Arsenic slag composition Cu=33.61%, As=18.22%, copper arsenic is than being Cu: As=1.845: 1.
Embodiment 3: bulking liquor contains composition: Cu=22.03g/L, As=12.54g/L, Cu: As=1.757: 1.Bulking liquor flow 4.0m
3/ h.62 ℃ of circulation fluid temperature.24 of electrodeposition dearsenification grooves.Dearsenification electric current 9.0KA.Terminal point liquid composition Cu=1.09g/L, As=1.28g/L.Arsenic slag composition Cu=32.10%, As=17.01%, copper arsenic is than being Cu: As=1.887: 1.
Embodiment 4: bulking liquor contains composition: Cu=24.85g/L, As=15.04g/L, Cu: As=1.652: 1.Bulking liquor flow 4.0m
3/ h.65 ℃ of circulation fluid temperature.24 of electrodeposition dearsenification grooves.Dearsenification electric current 9.0KA.Terminal point liquid composition Cu=1.66g/L, As=1.71g/L.Arsenic slag composition Cu=39.24%, As=20.86%, copper arsenic is than being Cu: As=1.881: 1.
Claims (4)
1, the continuous electrodeposition dearsenification method of circulation in parallel, electrolytic solution is purified dearsenification, it is characterized in that: electrolytic solution flows for parallel circulating type between electrodeposition dearsenification groove, heating cycle liquid, temperature is controlled at 60～66 ℃, electrodeposition dearsenification process is carried out comprehensive fluid infusion, and the bulking liquor flow equates that with the liquid effluent flow bulking liquor flow control is at 1～20m
3Between/the h, dearsenification cathode current density control 195～320A/m
2, bulking liquor copper arsenic is controlled at Cu: As=1.5～3: 1～1.5; The part electrolyzer is as the terminal point groove, and the terminal point groove is discharged the solution copper ion concentration and is controlled at Cu
2+=0.5～2.5g/L by control dearsenification bulking liquor, circulation fluid, terminal point liquid effluent, makes arsenic and copper formation arsenical copper Cu in the dearsenification process
2As, Cu
3As, and generate Cu as far as possible
2As.
2, according to the continuous electrodeposition dearsenification method of the described circulation in parallel of claim 1, it is characterized in that: bulking liquor is any one in liquid behind copper sulfate mother liquor, the decopper(ing), the electrolytic solution, or the mixed solution between them.
3, according to the continuous electrodeposition dearsenification method of the described circulation in parallel of claim 1, it is characterized in that: the used negative electrode of electrodeposition dearsenification is complete copper anode of profile or anode scrap.
4, the continuous electrodeposition dearsenification method of circulation in parallel according to claim 1, it is characterized in that: electrodeposition dearsenification groove is divided into terminal point groove and non-terminal point groove two classes, and terminal point groove solution is discharged system.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB200410021941XA CN1309849C (en) | 2004-02-27 | 2004-02-27 | Method of dearsenic by parallel circulating continuous electric formation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB200410021941XA CN1309849C (en) | 2004-02-27 | 2004-02-27 | Method of dearsenic by parallel circulating continuous electric formation |
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| Publication Number | Publication Date |
|---|---|
| CN1560289A CN1560289A (en) | 2005-01-05 |
| CN1309849C true CN1309849C (en) | 2007-04-11 |
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|---|---|---|---|
| CNB200410021941XA Expired - Lifetime CN1309849C (en) | 2004-02-27 | 2004-02-27 | Method of dearsenic by parallel circulating continuous electric formation |
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1321200C (en) * | 2005-12-23 | 2007-06-13 | 朱永文 | Method for separating copper, arsenic and zinc from copper-smelting high-arsenic flue dust sulphuric acid leach liquor |
| CN101906654B (en) * | 2010-07-19 | 2013-02-13 | 葫芦岛锌业股份有限公司 | Method for purifying copper electrolyte with minimal chemical reacting dose |
| CN103526230B (en) * | 2013-10-08 | 2015-12-09 | 铜陵有色金属集团股份有限公司金昌冶炼厂 | A kind of method of cleaning copper electrolyte processing efficient production high-quality cathode copper |
| CN111018211B (en) * | 2018-10-09 | 2023-04-18 | 昆明理工大学 | Method for removing arsenic by adding zinc powder into ultrasonic-enhanced waste acid |
| CN110453246B (en) * | 2019-08-28 | 2021-03-23 | 中南大学 | Method for in-situ synthesis of copper-arsenic alloy from copper electrolyte |
| CN111254463B (en) * | 2020-03-10 | 2021-05-04 | 吉林紫金铜业有限公司 | Decoppering system |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU1668481A2 (en) * | 1989-04-11 | 1991-08-07 | Норильский горно-металлургический комбинат им.А.П.Завенягина | Method of processing spent solution from electrolytic refining of copper |
| WO2001020062A1 (en) * | 1999-09-10 | 2001-03-22 | Mitsui Mining And Smelting Co., Ltd. | High current density electrolytic decomposition process for copper |
| CN1455007A (en) * | 2003-01-16 | 2003-11-12 | 云南锡业集团有限责任公司 | Arsonium-containing cupric sulfide concentrate smelting process by wet method |
| CN1465724A (en) * | 2002-10-31 | 2004-01-07 | 云南铜业科技发展股份有限公司 | Wet method copper-extracting process |
-
2004
- 2004-02-27 CN CNB200410021941XA patent/CN1309849C/en not_active Expired - Lifetime
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU1668481A2 (en) * | 1989-04-11 | 1991-08-07 | Норильский горно-металлургический комбинат им.А.П.Завенягина | Method of processing spent solution from electrolytic refining of copper |
| WO2001020062A1 (en) * | 1999-09-10 | 2001-03-22 | Mitsui Mining And Smelting Co., Ltd. | High current density electrolytic decomposition process for copper |
| CN1465724A (en) * | 2002-10-31 | 2004-01-07 | 云南铜业科技发展股份有限公司 | Wet method copper-extracting process |
| CN1455007A (en) * | 2003-01-16 | 2003-11-12 | 云南锡业集团有限责任公司 | Arsonium-containing cupric sulfide concentrate smelting process by wet method |
Non-Patent Citations (1)
| Title |
|---|
| 铜电解净液过程中砷的脱除 丁昆，华宏全，有色金属，第5期 2003 * |
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