CN1032703C - Method for removal of copper from electrolytic nickel anodic liquid - Google Patents
Method for removal of copper from electrolytic nickel anodic liquid Download PDFInfo
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- CN1032703C CN1032703C CN 94107298 CN94107298A CN1032703C CN 1032703 C CN1032703 C CN 1032703C CN 94107298 CN94107298 CN 94107298 CN 94107298 A CN94107298 A CN 94107298A CN 1032703 C CN1032703 C CN 1032703C
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- electrolysis anode
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Abstract
The present invention relates to a method for removing copper from electrolytic nickel anodic liquid, which is suitable for removing copper of electrolytic nickel anodic liquid which adopts a sulfate-chloridate (or pure chloride) system. The method for removing copper is characterized in that active nickel sulfide reacts with copper ions of electrolytic nickel anodic liquid to be processed in a reduction mode to produce copper sulfide deposit; copper-removal liquid containing less than 0.002 g/l of copper and copper-removal slag containing 70 to 73% of copper and larger than 20 of Cu/Ni are separated by filtration. The nickel content in the slag is low, and the quantity of the slag is less. The method can be directly used for copper smelting, and the direct yield of metal nickel-copper is enhanced. The method for removing copper has the advantages of no introduction of any impurity no pollution, simple operation and continuous production.
Description
The copper-removing method of nickle electrolysis anode solution is applicable in the nickel smelting process, adopts vitriol--the copper removal of nickel (cobalt) the electrolytic anode liquid of muriate (or all-chloride) system.
Copper content acquires a certain degree and can have a strong impact on the quality of electrolytic nickel in the nickle electrolysis anode solution, and people are striving to find the method for the copper removal of effective practicality always.At present, existing a lot of methods such as substitution method, hydrolysis method, extraction process, sulphide precipitation etc. are wherein used maximum have substitution method and hydrogen sulfide precipitation methods.The nickel powder substitution method is adopted by a lot of nickel factory, but the preparation cost height of nickel powder, the metal direct yield of nickel is low, nickeliferous height in the slag, and Cu/Ni is low in the slag, is unfavorable for the recovery of copper.Hydrogen sulfide precipitation method copper removal speed is fast, nickeliferous low in the slag, but hydrogen sulfide is a kind of hypertoxic gas, leaks easily, and environment structure is threatened, a small amount of suction can make the people suffocate.Also there is minority producer to adopt nickel sulfide concentrate to add the copper-removing method of the anode sludge, this method advantage is to need not outer adding medicine, process is simple, shortcoming is the nickel sulfide concentrate poor activity, sulfonium ion can not react with cupric ion effectively, the quantity of slag is big, the slag cupric is low, Cu/Ni only is 0.5 in the slag, to the nickle electrolysis anode solution copper removal with to remove the extraction of copper in the copper ashes all unfavorable.
The object of the present invention is to provide that a kind of copper removal is effective, pollution-free, the copper-removing method of a kind of nickle electrolysis anode solution of nickeliferous low, Cu/Ni is high, direct yield height simple to operate, nickel helps copper simultaneously recovery in the slag.
The copper-removing method of nickle electrolysis anode solution of the present invention is characterized in that:
A. sodium sulphite and the reaction of a certain amount of nickle electrolysis anode solution are produced the decoppering agent active nickel sulfide, its chemical reaction is:
Reaction conditions is: sodium sulphite concentration: 80～120g/l,
Control reaction temperature: 15～30 ℃
The pH value of control reaction end is 8.5～9.0,
Stir its granularity of control in 1～10um scope.
B. S-WAT is joined in the nickle electrolysis anode solution that desire handles, wherein bivalent cupric ion is reduced to univalent copper ion, its chemical reaction is:
Reaction conditions is:
The add-on of S-WAT is by 1.1～1.4 times of the theoretical amount of its chemical reaction
Temperature of reaction is 55～70 ℃,
5～10 minutes reaction times,
Reduction terminal point current potential is 230～190mv (SCE),
C. the active nickel sulfide that makes is joined and reduce in the nickle electrolysis anode solution of handling, carry out copper removal, its chemical reaction is:
Reaction conditions is:
The add-on of active nickel sulfide is 1.10～1.30 times of theoretical amount,
Temperature of reaction is 55～70 ℃,
Reaction times is 5～20 minutes,
The reaction process CONTROLLED POTENTIAL is-110～-50mv,
Again after filtration liquid and remove copper ashes behind the copper removal.
The present invention index advanced person that compared with prior art possesses skills, reagent consumption is few, and is pollution-free, copper removal is effective, cupric＜0.002g/l in the liquid behind the copper removal, copper content height in the slag can reach 70～73%, Cu/Ni in the slag＞20, nickel content is low, and the quantity of slag is few, and can be directly used in the copper smelting, improve the metal direct yield of ambrose alloy, system is not introduced any impurity, simple to operate, can realize the quantity-produced advantage.
Fig. 1 is the copper-removing method process flow sheet of nickle electrolysis anode solution.
The copper-removing method operational process of craft and the reaction mechanism of nickle electrolysis anode solution are specific as follows.
At first sodium sulphite is joined in the nickle electrolysis anode solution Ni in sodium sulphite and the solution
2+Reaction generates nickelous sulfide, and chemical reaction is:
The control reaction conditions is: the add-on of S-WAT is by 1.1～1.4 of the theoretical amount of its chemical reaction, temperature of reaction is 55～70 ℃, 5～10 minutes reaction times, control reduction terminal point current potential is 230～190mv (SCE), the active nickel sulfide that has made is joined in the as-reduced nickle electrolysis anode solution, the solid copper sulfide precipitation that reaction generates can reach the purpose of copper removal after filtering, reaction conditions is: the add-on of nickelous sulfide is theoretical amount ((in Cu) 0.55～0.65 times, temperature of reaction is 55～70 ℃, reaction times is 5～20 minutes, the reaction process CONTROLLED POTENTIAL is-100～-50mv.The index that nickle electrolysis anode solution removes behind the process for copper can reach: [Cu]＜0.002g/l, slag cupric 70～73%, Cu/Ni in the slag＞20.
The Cu that uses in the copper-removing method of nickle electrolysis anode solution
2+Reductive agent can also be SO
2
Because the nickelous sulfide that control certain reaction condition generates obtains the superfine nickelous sulfide slurry of particle through stirring, has higher chemically reactive, can effectively remove the cupric ion in the solution.But because the cupric ion in the nickel electrolyte has stronger oxidisability, directly act on, can cause the S among the NiS with active nickel sulfide
2-Oxidation generates S
2, form integument on sulfuration nickel shot surface, can greatly influence the activity of nickelous sulfide, so the nickle electrolysis anode solution that desire is handled makes the cupric ion reduction and generates CuCl with S-WAT or sulphur dioxide reduction earlier
2 -(or CuCl
3 2-), active nickel sulfide and CuCl
2 -Replacement(metathesis)reaction takes place, and cupric ion is with Cu
2The form of S is precipitated out.Because eliminated the diffusional resistance of active nickel sulfide, copper removal is effective, speed of response is fast, and dosing is few, and the liquid cupric is low behind the copper removal, and Cu/Ni height in the slag removes copper ashes and can directly enter the copper smelting process, and cost is low, and is profitable.
1 preparation condition is to the active influence of nickelous sulfide
1.1 the nickelous sulfide preparation temperature is to the active influence of nickelous sulfide
The synthetic back of nickelous sulfide was stirred 1500 rev/mins of rotating speeds 2 minutes
The copper removal condition for surveys: the S-WAT consumption is 1.2 times of theoretical amount, the nickelous sulfide consumption is 0.58 times (in Cu) for theoretical consumption, 60 ℃ of copper removal temperature, 5 minutes recovery times, 10 minutes copper removal time, the result is as follows: behind the numbering preparation temperature copper removal in the melt cinder
(℃) cupric (mg/l) Cu/Ni D2-1 20 6.38 224.25 D2-3 30 9.08 450.40
1.2 churning time is to the active influence of nickelous sulfide
20 ℃ of nickelous sulfide preparation temperatures, except that the nickelous sulfide consumption was 0.6 times of theoretical amount, other condition was with 1.1 in the copper removal condition for surveys.Behind the numbering preparation temperature copper removal in the melt cinder
(℃) cupric (mg/l) Cu/Ni) D4-1 0 33.80 15.19 D4-4 4 0.58 46.25
1.3 the relation of (the last liquid after nickelous sulfide is synthetic) nickeliferous and pH behind the heavy nickel
pH?????????????????8.0???8.5??9.0???9.5
Liquid contains Nj (mg/l) 475.8 43.4 4.0 3.76 behind the copper removal
2 reduction copper removal test conditions and results
2.1 S-WAT consumption, nickelous sulfide consumption, temperature, time, stirring and copper removal acidity influence the nickelous sulfide preparation condition to the copper removal index, with 3 times of anolyte dilutions, normal temperature is synthetic, precipitation stirs 2 minutes, rotating speed 1500 changes/(table is seen the literary composition back)
2.2 S-WAT consumption, nickelous sulfide consumption are to the influence of current potential and copper removal index
The sodium sulphite preparation condition is with 2.1.
Copper removal condition: 60 ℃ of PH2 of temperature～5 minutes 3 recovery times
250 rev/mins of 10 minutes copper removal time mixing speed (table is seen the literary composition back)
Test-results is as follows:
* consumption is the multiple of theoretical consumption
E1 is reduction terminal point current potential
E2 is a copper removal terminal point current potential
The copper-removing method of nickle electrolysis anode solution of the present invention can be realized continuous production, helps realizing automatic control.
Method of the present invention also is applicable to the copper removal of cobalt electrolytic anode liquid, and its reaction mechanism is identical.
Numbering sulfurous acid nickelous sulfide temperature-time rotating speed
Sodium consumption consumption * (℃) (min) (min
-1)
D9-7??????*???????0.62???????70???????5??????200
D9-13????1.1??????0.56???????70??????10??????400
D9-16????1.3??????0.65???????55??????15??????200
Original acidity (pH) [Cu] is Cu/Ni in the slag (mg/l))
2～3???????????0.38????????23.82
2～3???????????0.83???????272.89
4～5???????????0.28????????23.61
* consumption is the multiple of theoretical consumption
Numbering S-WAT consumption * nickelous sulfide consumption * E1 (mv) E2 (mv) [Cu] is (in the mg/l slag
)???????Cu/Ni???D12-2????????1.1?????????????0.58?????????222????????2???????1.85??????47.58???D12-6????????1.2?????????????0.56?????????219???????-76??????0.47?????102.86???D12-15???????1.5?????????????0.62?????????213???????-136?????0.32??????27.38???D13-6????????1.4?????????????0.68?????????217???????-123?????0.55??????25.45
Claims (3)
1. the copper-removing method of nickle electrolysis anode solution especially for the copper-removing method of the nickle electrolysis anode solution of vitriol-muriate (or all-chloride) system, is characterized in that its process is made up of the following step:
(a) sodium sulphite and the reaction of a certain amount of nickle electrolysis anode solution are produced the decoppering agent active nickel sulfide, processing condition are:
Sodium sulphite concentration: 80～120g/l,
Control reaction temperature: 15～30 ℃,
The pH value of control reaction end is 8.5～9.0,
Stirring makes the granularity of active nickel sulfide of generation in 1～10um scope;
(b) S-WAT is joined in the nickle electrolysis anode solution of desire processing, the bivalent cupric ion in the nickle electrolysis anode solution is reduced to univalent copper ion, processing condition are:
The add-on of S-WAT is 1.1～1.4 times of theoretical amount of its chemical reaction, and temperature of reaction is 55～70 ℃
Temperature of reaction is 55～70 ℃,
5～10 minutes reaction times,
Control reduction terminal point current potential is 230～190mV (SCE);
(c) active nickel sulfide that makes joined reduce in the nickle electrolysis anode solution of handling, carry out copper removal, filter liquid and remove copper ashes behind the copper removal, processing condition are:
The add-on of active nickel sulfide is 1.10～1.30 times of theoretical amount, and temperature of reaction is 55～70 ℃.
Reaction times is 55～20 minutes,
The reaction process CONTROLLED POTENTIAL is-110～-50mv.
2. the copper-removing method of nickle electrolysis anode solution according to claim 1 is characterized in that: to be reduced into the reductive agent that the method for univalent copper ion adopts can also be sulfurous gas to bivalent cupric ion in the nickle electrolysis anode solution.
3. the copper-removing method of nickle electrolysis anode solution according to claim 1 also can be used for the copper removal of cobalt electrolytic anode liquid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 94107298 CN1032703C (en) | 1994-06-29 | 1994-06-29 | Method for removal of copper from electrolytic nickel anodic liquid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 94107298 CN1032703C (en) | 1994-06-29 | 1994-06-29 | Method for removal of copper from electrolytic nickel anodic liquid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1100153A CN1100153A (en) | 1995-03-15 |
| CN1032703C true CN1032703C (en) | 1996-09-04 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 94107298 Expired - Fee Related CN1032703C (en) | 1994-06-29 | 1994-06-29 | Method for removal of copper from electrolytic nickel anodic liquid |
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| CN (1) | CN1032703C (en) |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100378233C (en) * | 2004-08-30 | 2008-04-02 | 金川集团有限公司 | Process for cleaning decopper nickel electrolytic solution |
| CN100510195C (en) * | 2006-03-17 | 2009-07-08 | 金川集团有限公司 | Method for control PH value of nickel powder electrolyte |
| CN102181882B (en) * | 2011-04-09 | 2012-11-21 | 中南大学 | Method for purifying copper electrolyte by regulating valence state |
| CN103022528B (en) * | 2012-12-04 | 2015-06-03 | 中国科学院金属研究所 | Method for cleanly removing copper ions in copper-bearing vanadium solution |
| CN103668323B (en) * | 2013-12-12 | 2016-06-08 | 昆明理工大学 | The method of a kind of electrolysis-segmentation electrodeposition method Treatment of Copper nickel materials |
| CN103820809B (en) * | 2014-02-28 | 2017-03-01 | 金川集团股份有限公司 | A kind of copper-removing method |
| CN104694751B (en) * | 2015-03-20 | 2017-06-23 | 西安瑞鑫科金属材料有限责任公司 | A kind of method of removing chloride ion in leachate from zinc hydrometallurgy |
| CN106191917A (en) * | 2016-08-04 | 2016-12-07 | 浙江工业大学义乌科学技术研究院有限公司 | A kind of impurity removal process of nickle electrolysis anode solution |
| CN111411229B (en) * | 2020-04-29 | 2021-04-09 | 长沙华时捷环保科技发展股份有限公司 | Process for efficiently separating nickel and copper in nickel electrolyte |
| CN113061724B (en) * | 2021-03-09 | 2022-10-18 | 金川集团股份有限公司 | Method for eluting nickel sulfide and removing nickel and chloride ions in copper tailings |
| CN113151863A (en) * | 2021-03-18 | 2021-07-23 | 金川集团股份有限公司 | Method for removing copper ions in nickel production process by electrodeposition |
| CN113322489A (en) * | 2021-06-23 | 2021-08-31 | 阳谷祥光铜业有限公司 | Method for preparing electrodeposited nickel by using crude nickel sulfate |
| CN114517309B (en) * | 2022-03-15 | 2023-09-26 | 金川镍钴研究设计院有限责任公司 | Nickel supplementing and decoppering method in nickel electrolysis production system |
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- 1994-06-29 CN CN 94107298 patent/CN1032703C/en not_active Expired - Fee Related
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| CN1100153A (en) | 1995-03-15 |
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