CN103898559B - One utilizes ionic liquid electrodialysis to remove the method for As, Sb in copper electrolyte - Google Patents
One utilizes ionic liquid electrodialysis to remove the method for As, Sb in copper electrolyte Download PDFInfo
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- CN103898559B CN103898559B CN201410132012.XA CN201410132012A CN103898559B CN 103898559 B CN103898559 B CN 103898559B CN 201410132012 A CN201410132012 A CN 201410132012A CN 103898559 B CN103898559 B CN 103898559B
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- CN
- China
- Prior art keywords
- copper electrolyte
- ionic liquid
- electrodialysis
- cathode
- compartment
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 32
- 239000010949 copper Substances 0.000 title claims abstract description 32
- 239000003792 electrolyte Substances 0.000 title claims abstract description 27
- 239000002608 ionic liquid Substances 0.000 title claims abstract description 18
- 238000000909 electrodialysis Methods 0.000 title claims abstract description 16
- 229910052787 antimony Inorganic materials 0.000 title claims description 12
- 229910052785 arsenic Inorganic materials 0.000 title claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N HCl Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000000605 extraction Methods 0.000 claims abstract description 7
- 239000003014 ion exchange membrane Substances 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-M chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 5
- -1 methyl butyl Chemical group 0.000 claims description 5
- 239000005092 Ruthenium Substances 0.000 claims description 4
- 150000002500 ions Chemical class 0.000 claims description 4
- KJTLSVCANCCWHF-UHFFFAOYSA-N ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 4
- 229910052707 ruthenium Inorganic materials 0.000 claims description 4
- 239000010936 titanium Substances 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 3
- 239000003011 anion exchange membrane Substances 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 239000003957 anion exchange resin Substances 0.000 claims 1
- 125000000129 anionic group Chemical group 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 13
- 230000003247 decreasing Effects 0.000 abstract description 4
- 239000007788 liquid Substances 0.000 abstract description 3
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- 229910017253 AsO Inorganic materials 0.000 description 19
- 125000001317 arsoryl group Chemical group *[As](*)(*)=O 0.000 description 17
- 239000012535 impurity Substances 0.000 description 7
- 230000005684 electric field Effects 0.000 description 5
- 239000008151 electrolyte solution Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000001172 regenerating Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- 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
Abstract
One of the present invention utilizes ionic liquid to remove As in copper electrolyte, the method of Sb, comprise the following steps: remove in system in electrodialysis of the present invention, copper electrolyte puts into cathode compartment, certain density ionic liquid and hydrochloric acid put into anolyte compartment, in use constantly add, keep certain temperature and pH value, under certain electrodialysis voltage, react certain hour.The copper electrolyte of cathode compartment circulates again and again, anolyte compartment's effluent liquid puts into an abstraction pool, extract with extraction agent, thus in copper electrolyte the decreasing ratio of As up to 70%, the decreasing ratio of Sb is up to 50%, and the method can process copper electrolyte continuously, and technical process is simple, processing condition require low, environmental protection and saving.
Description
Technical field
The present invention relates to a kind of electrodialysis process, especially relate to one and utilize ionic liquid to remove the electrodialysis process that in copper electrolyte, As, Sb use.
Background technology
In the Extraction metallurgy process of copper, be raw material with Copper Ores, generally obtain blister copper by pyrometallurgical smelting, the impurity wherein mainly comprised has: As, Sb, Bi, Fe, Pb, Zn, Ni etc., and wherein the impact of As, Sb anticathode copper mass is larger.In anode copper electrorefining processes, the impurity in anode dissolves with copper and enters electrolytic solution, and the impurity of enrichment gathers on negative electrode by the mode of mechanical entrainment and chemical precipitation, thus causes impurity content exceeding index in cathode copper.Therefore regularly evolution removal of impurities must be carried out to electrolytic solution, to meet the requirement of cupric electrolysis.Electrolytic refining course of copper, As, Sb enter electrolytic solution with anode dissolution, mainly with AsO
4 3-, AsO
3 3-, SbO
3 3-and SbO
4 3-state exists.At present, the method for domestic and international developed cleaning copper electrolyte removal of impurities mainly comprises electrodip process, absorption method, the precipitator method, solvent extraction and ion exchange method etc.The present invention, mainly under electric field action, utilizes the selection of film to reach cupric ion and foreign ion AsO through this feature
4 3-, AsO
3 3-, SbO
3 3-and SbO
4 3-separation, recycling extraction process carrys out enrichment foreign ion, and do not need to process in addition electrolytic solution, operation is simple.
Summary of the invention
The object of the present invention is to provide one to utilize ionic liquid electrodialysis to remove the method for As, Sb in copper electrolyte, effectively can simplify Impurity removal program in copper electrolyte, improve the performance of electrolytic solution further.
Method of the present invention is in the electrodialyzer of a two room, utilizes the characteristic of ion-exchange membrane, removes As, Sb in copper electrolyte continuously.Concrete grammar is as follows:
As shown in drawings, the electrodialysis that the present invention is made up of cathode compartment, negative electrode, anolyte compartment, anode, ion-exchange membrane, rectifier power source, agitator and abstraction pool removes system, copper electrolyte puts into cathode compartment, ionic liquid methyl butyl imidazolitm chloride (molecular formula is BMIMCl) and hydrochloric acid put into anolyte compartment, in use constantly add, arrange the agitator of a controllable speed in anolyte compartment, temperature is 30-50 DEG C, pH is 0.5-1.0.It is characterized in that being coated with ruthenium noble electrode for anode and cathode with titanium, current density is 1 ~ 6A/dm
2.The effluent liquid of room, negative electrode pole still returns original stationary tank, circulates again and again, and anolyte compartment's effluent liquid puts into an abstraction pool, uses petroleum ether extraction.Direct current is provided by a silicon commutating power supply, and electrodialysis voltage is 5.0 ~ 20V, and the reaction times is 1.5 ~ 8 hours.
Principle reaction of the present invention is as follows:
AsO in cathode compartment copper electrolyte
4 3-, AsO
3 3-, SbO
3 3-and SbO
4 3-ion, under the effect of electric field, enters into the hydrochloric acid containing ionic liquid BMIMCl in anolyte compartment through cavity block, the AsO in cathode compartment copper electrolyte
4 3-, AsO
3 3-, SbO
3 3-and SbO
4 3-after ion and OH exchange, AsO
4 3-, AsO
3 3-, SbO
3 3-and SbO
4 3-ion enters anolyte compartment by cavity block under the effect of electric field, and the copper electrolyte be purified directly returns original stationary tank from outlet, and AsO
4 3-, AsO
3 3-, SbO
3 3-and SbO
4 3-ion reacts in the hydrochloric acid containing ionic liquid BMIMCl, generates a kind of new ionic liquid BMIMH
2asO
4, BMIMAsCl
4, BMIMSbCl
6, BMIMSbCl
4, its reaction mechanism is:
BMIMCl+AsO
4 3-+2HCl→BMIMH
2AsO
4+3Cl
-
BMIMCl+AsO
3 3-+6HCl→BMIMAsCl
4+3H
2O+3Cl
-
BMIMCl+SbO
3 3-+6HCl→BMIMSbCl
4+3H
2O+3Cl
-
BMIMCl+SbO
4 3-+8HCl→BMIMSbCl
b -+4H
2O+3Cl
-
In above-mentioned electrodialysis process, under the effect of DC electric field, the feature of ion-exchange membrane is that anion-exchange membrane only allows anion-permeable, so can complete the carrying out of reaction, and owing to have employed homogeneous ion-exchange membrane, make whole process have more stain resistance and react more stable.
Feature of the present invention is:
(1) whole device can process copper electrolyte continuously, avoids periodical operation;
(2) regenerative process is easy to control, and preparation technology's flow process is simple, and processing condition require low;
(3) facility compact, the recovery time is short, thus can save a large amount of productive expenses.
Accompanying drawing explanation
Figure removes system for electrodialysis of the present invention.
Embodiment
As shown in drawings, the present invention removes in system in the electrodialysis be made up of cathode compartment, negative electrode, anolyte compartment, anode, ion-exchange membrane, rectifier power source, agitator and abstraction pool, anode and negative electrode adopt titanium to be coated with ruthenium metal electrode, anolyte compartment adds the 1mol/l ionic liquid methyl butyl imidazolitm chloride aqueous solution, regulate pH value to be 0.6 with concentrated hydrochloric acid, current density is 4A/dm
2, electrodialysis voltage is 16V.Containing AsO
4 3-, AsO
3 3-, SbO
3 3-and SbO
4 3-the copper electrolyte of ion utilizes potential difference through under meter from stationary tank, and flow rate control, at 50L/h, from up to down flows through and of the present inventionly removes in the electrodialysis unit of As, Sb in copper electrolyte, the AsO in cathode compartment copper electrolyte
4 3-, AsO
3 3-, SbO
3 3-and SbO
4 3-ion is under the effect of electric field, anolyte compartment is entered into through cavity block, react with ionic liquid methyl butyl imidazolitm chloride and hydrochloric acid under stirring, reaction times is 7 hours, the new ionic liquid generated draws anolyte compartment by recycle pump 2, carry out the extraction of ionic liquid in containing the abstraction pool of sherwood oil, the copper electrolyte recycle pump 1 be purified directly pumps in copper electrolyte storage tank from cathode chamber outlet, in copper electrolyte, the decreasing ratio of As is the decreasing ratio of about 70%, Sb is thus about 50%.
Claims (4)
1. As in a copper electrolyte, the method that Sb removes continuously, it is characterized in that: remove in system in electrodialysis, anionic ion exchange membrane is homogeneous ion-exchange membrane, and it is anode and cathode that titanium is coated with ruthenium noble electrode, and copper electrolyte, ionic liquid methyl butyl imidazolitm chloride and hydrochloric acid are raw material, the direct current passing to certain hour removes As in copper electrolyte continuously, Sb, anolyte compartment draws and enters abstraction pool sherwood oil containing the ionic liquid of As, Sb and carry out extraction treatment.
2. removal methods according to claim 1, is characterized in that: be provided with anolyte compartment, cathode compartment, strong base anion exchange membrane, agitator, rectifier power source and abstraction pool, and anode and negative electrode are that titanium is coated with ruthenium inert metal electrode.
3. removal methods according to claim 1, it is characterized in that: ionic liquid methyl butyl imidazolitm chloride and hydrochloric acid add the anolyte compartment of electrodialyzer, containing As in copper electrolyte, the ion of Sb from cathode compartment by the strong basic type anion-exchange resin film between cathode and anode room, the reacted ionic liquid containing As, Sb enters abstraction pool sherwood oil and carries out extraction treatment.
4. removal methods according to claim 1, is characterized in that: removal temperature is 30-50 DEG C, pH is 0.5-1.0, and current density is 1 ~ 6A/dm
2, electrodialysis voltage is 5.0 ~ 20V, and the reaction times is 1.5 ~ 8 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410132012.XA CN103898559B (en) | 2014-03-28 | 2014-03-28 | One utilizes ionic liquid electrodialysis to remove the method for As, Sb in copper electrolyte |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410132012.XA CN103898559B (en) | 2014-03-28 | 2014-03-28 | One utilizes ionic liquid electrodialysis to remove the method for As, Sb in copper electrolyte |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103898559A CN103898559A (en) | 2014-07-02 |
| CN103898559B true CN103898559B (en) | 2016-04-06 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410132012.XA Active CN103898559B (en) | 2014-03-28 | 2014-03-28 | One utilizes ionic liquid electrodialysis to remove the method for As, Sb in copper electrolyte |
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|---|---|
| CN (1) | CN103898559B (en) |
Families Citing this family (1)
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|---|---|---|---|---|
| CN106119547A (en) * | 2016-07-20 | 2016-11-16 | 中国恩菲工程技术有限公司 | A kind of method reclaiming copper in the outer waste discharge acid of Copper making system for preparing sulfuric acid |
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|---|---|---|---|---|
| CN103332764B (en) * | 2013-06-08 | 2015-12-23 | 河北工程大学 | A kind of apparatus and method removing heavy metal ion in water |
| CN103482793B (en) * | 2013-09-26 | 2015-09-16 | 昆明理工大学 | A kind of dirty sour method of comprehensive utilization |
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| Publication number | Publication date |
|---|---|
| CN103898559A (en) | 2014-07-02 |
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Effective date of registration: 20180412 Address after: High tech Zone Hefei city Anhui province 230088 Tianzhi Road No. 19 original animation Park South Building Room 1136 Patentee after: Hefei easy Valley Intellectual Property Operation Co. Ltd. Address before: 246001 Anqing, Daguan District, Anhui, Hunan Road, No. 128 Patentee before: Anqing Normal University |
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Effective date of registration: 20180929 Address after: 244002 695 north section of Taishan Avenue, Tongling, Anhui. Patentee after: Tongling is with flying Science and Technology Ltd. Address before: 230088 room 1136, South Tower, original animation Park, 19 Tian Zhi Road, Hefei High-tech Zone, Anhui Patentee before: Hefei easy Valley Intellectual Property Operation Co. Ltd. |