CN1598012A - Process for cleaning decopper nickel electrolytic solution - Google Patents
Process for cleaning decopper nickel electrolytic solution Download PDFInfo
- Publication number
- CN1598012A CN1598012A CNA2004100568942A CN200410056894A CN1598012A CN 1598012 A CN1598012 A CN 1598012A CN A2004100568942 A CNA2004100568942 A CN A2004100568942A CN 200410056894 A CN200410056894 A CN 200410056894A CN 1598012 A CN1598012 A CN 1598012A
- Authority
- CN
- China
- Prior art keywords
- nickel
- copper
- thiosulfate
- electrolyte
- solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
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
Landscapes
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention relates to a purifying and removing impurity method with nickel electrolyte in the process of wet way metallurgy technics, especially purifying and removing copper with nickel electrolyte. It is adding NiS2O3 into nickel electrolyte to purify and remove copper, the technics process is adding NiS2O3 into nickel electrolyte according to the proportion of S2O3 2-/Cu2+ =4.4-7:1, at the temperature of 65-70deg.C, adding acid and adjusting Ph between 0.5 and 2, the stirring reaction time is 30-40min, finally separating and producing the deposition of CuS, attaining the liquid of purifying and removing copper. The thiosulfate is easily dissolved in water, it could not cause high content of nickel in the copper residues even excessive appending when removing copper, it is different from removing copper with nickel, nickel concentrate and sulfureted nickel, therefore with low nickel content in residues.
Description
Technical Field
A method for removing copper from nickel electrolyte relates to a method for purifying and removing impurities from the electrolyte in the process of producing metallic nickel by adopting a hydrometallurgical process, in particular to a method for purifying and removing copper from the nickel electrolyte.
Background
In wet nickel electrolysis, the solution after iron removal generally comprises the following components: ni: 65-75 g/L, Cu: 0.3-0.6 g/L, Fe<0.001g/L, SO4 2-：100～120g/L，Cl-: 80-90 g/L. In order to ensure the quality of electrolytic nickel, a method of adding anode mud into nickel concentrate is continuously adopted to remove copper, the method has good copper removal effect and high reaction speed, and can basically meet the production requirements. However, the poor activity of the nickel concentrate causes incomplete replacement of the nickel concentrate, so that the nickel content of the copper-removing slag is high, the average nickel content is as high as 40%, the copper content is only 20%, and the slag amount is large, thereby directly influencing the direct yield of production.
In recent years, in order to improve the direct recovery rate of nickel, people adopt a copper slag chlorine full leaching process to leach all produced copper slag, so that the direct recovery rate of a workshop is greatly improved. However, whenthe nickel in the copper slag is leached, the copper in the slag is also leached into a solution system, which undoubtedly causes vicious circulation of the copper in the solution system, and although the solution is subjected to liquid making and copper removal firstly, the capacity is limited, which inevitably causes the circulation accumulation of the copper in the solution, and brings a lot of difficulties to production. People are looking for a more effective copper removal method.
At present, there are many methods for removing copper in the hydrometallurgy of nickel and cobalt leaching, and there are nearly ten kinds of sulfidation methods, except the currently adopted method for removing copper by adding anode mud into nickel concentrate, there are also methods for removing copper by adding sodium thiosulfate, hydrogen sulfide, sodium sulfide, active nickel sulfide, nickel powder, nickel pellets, sulfur dioxide and sulfur, etc. Among them, sodium thiosulfate has good copper removal effect, short reaction time and good working conditions, but brings disadvantages to system balance due to bringing a large amount of sodium ions into a solution system.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a method for purifying and removing copper from nickel electrolyte, which can deeply remove copper, effectively reduce nickel content in slag, reduce slag amount, improve direct yield, has loose technical conditions and is easy to operate.
The purpose of the invention is realized by the following technical scheme.
A method for removing copper from nickel electrolyte is characterized in that nickel thiosulfate is added into the nickel electrolyte as a copper removing agent for copper removal and purification, and the technical process is as follows: in nickel electrolyte as S2O3 2-/Cu2+Adding nickel thiosulfate in a molar ratio of 4.4-7: 1, and adding acid at 65-70 ℃ to adjust the pH value to 0.5-2; stirring for reaction for 30-40min, and filtering to separate out the generated CuS precipitate to obtain the copper-removed solution.
By adopting the copper removal method, the copper content of the copper-removed liquid is less than 0.001g/l, the nickel content of the copper slag is extremely low, and the copper-nickel ratio reaches more than 100: 1. The existing copper removing equipment can be used for production without great change, and can meet the copper removing requirement of producing the electrolytic nickel.
The copper removing method of the copper removing agent is suitable for removing copper by using the nickel electrolysis cleaning solution, the technical conditions are loose, and the operation is easy for workers. The copper-nickel ratio in the copper slag after copper removal is far greater than 20: 1, the nickel content in the slag is less than 1%, the copper slag can completely enter a copper system as copper concentrate, an open circuit of copper is formed, the circulation of copper in nickel electrolysis is not caused, and the recovery rate and the direct recovery rate of nickel are improved. The method does not give liquidIs brought into other harmful ions and S is not completely reacted2O3 2-The stability of the ions is poor, and the ions are easily oxidized into sulfate ions by chlorine when entering the next cobalt removal process, so that the method does not bring adverse effects to the next electrolysis process.
The method adopts liquid nickel thiosulfate as a copper removing agent, and the production raw materials are new liquid of a nickel electrolysis system or solution containing nickel sulfate and part of solid nickel sulfate, Spowder and SO2Can also be produced as a byproduct in the nickel production process, and has convenient raw material sources. The copper removing agent of nickel thiosulfate produced by the new electrolytic solution, in which nickel is only used as the carrier of thiosulfate radical in the whole process, and when removing copper, it can be returned to nickel electrolytic system, and can raise Ni content in the electrolyte2+The concentration is 2-4 percentage points.
The thiosulfate and the sulfur-containing complex of the copper remover are easy to dissolve in water, and the nickel content of the copper slag is not increased even if excessive sulfur is added during copper removal, which is different from the copper removal of nickel powder, nickel concentrate and nickel sulfide, so that the nickel content of the slag is low. And the amount of copper slag is reduced to 1/4 at present, the process intensity is reduced, and the manpower and the energy consumption are saved. The thiosulfate of soluble nickel and the sulfur-containing complex are used for removing copper, so that sodium ions brought into the solution are avoided, and nickel in the slag is reduced. The copper content of the copper-removed liquid is less than 0.001g/L, the copper-nickel ratio in the copper slag is more than 20: 1, and the average ratio is 136: 1.
In the preparation of the nickel thiosulfate of the copper removing agent, the traditional synthetic method of the thiosulfate is used for reference: adding a proper amount of sulfur powder into a nickel sulfite solution, boiling together, and obtaining the nickel thiosulfate under the action of a catalyst. The specific operation steps are as follows: a proper amount of nickel carbonate is weighed and placed in a sulfurous acid solution, so that the nickel carbonate is firstly converted into nickel sulfite, and then excessive sulfur powder is added. Heating and refluxing for a certain time under the actionof a catalyst, cooling to room temperature, filtering to remove residues, and collecting filtrate. The detection proves that the filtrate contains a certain concentration of thiosulfate ions. Repeating the experiment, and when the concentration fluctuation is between 0.5-1.8 moL, the direct yield is 50% -75% in terms of nickel. The thiosulfate ion concentration was found to gradually decrease with the time of standing. After 24 hours, the concentration of the product is reduced by about 65 percent. With the precipitation of elemental sulphur. If a proper amount of antioxidant is added, the situation can be greatly improved.
In order to improve the product quality of the nickel thiosulfate and prepare stable nickel thiosulfate, a more reasonable preparation route is found. The mechanism is as follows:
due to BaSO4Ksp of (1.1X 10)-10And BaS2O3Ksp of (1) 8.0X 10-7. The above reaction is feasible. Directly introducing thiosulfate ions into the aqueous solution of nickel sulfate to react with nickel ionsAnd (3) carrying out a crude reaction, separating slag (sediment) from the solution after the reaction, separating nickel thiosulfate from the solution, and dehydrating and concentrating the nickel thiosulfate to obtain a nickel thiosulfate solution with any concentration and a solid crystal product. Experiments prove that the total recovery rate is not lower than 90%. Special measures are taken for liquid or solid products, which can maintain effective activity for a long time.
A method for purifying and decoppering nickel electrolyte is characterized in that a preparation process of adding a nickel thiosulfate decoppering agent into thenickel electrolyte is as follows: according to BaS2O3And NiSO4The molar ratio of the components is 1: 0.94, the reaction temperature is 35-40 ℃, the reaction time is 85-110min, and the liquid nickel thiosulfate copper remover is prepared.
A method for purifying and decoppering nickel electrolyte is characterized in that in the preparation process of adding a nickel thiosulfate decoppering agent into a nickel electrolyte solution, a concentrating agent ethanol is added into the prepared liquid nickel thiosulfate decoppering agent according to the proportion of 1: 2.5-4.5, and the reaction time is 24 hours, so that the solid nickel thiosulfate decoppering agent is prepared.
A method for removing copper from nickel electrolyte by purification is characterized in that a concentrating agent ethanol is added into liquid nickel thiosulfate with the concentration of 80-160g/L when a solid nickel thiosulfate copper removing agent is prepared.
Experiments prove that: the purity of the solid nickel thiosulfate decoppering agent has a certain relation with the concentration of the liquid nickel thiosulfate decoppering agent. The effect of the concentrating agent on the stability of the liquid nickel thiosulfate decoppering agent with higher concentration is shown.
The ionic product constants of barium sulfate and barium thiosulfate are respectively: 1.1X 10-10、8.0×10-7. By utilizing the difference of ion product, firstly, soluble thiosulfate is converted into barium thiosulfate, and then NiSO is controlled4Concentration and series of reaction conditions of (1), preparation of NiS by separation after secondary conversion2O3The solution is added with the concentration agent to prepare solid NiS2O3·xH2O, namely the copper removing agent of the nickel thiosulfate. Through analysis and identification, the prepared nickel thiosulfate copper remover is confirmed, and the main body is NiS2O3·6H2O, light green columnar crystals of pureThe degree is between 94% and 96%.
Through different detection means, the main body of the prepared solid nickel thiosulfate decoppering agent is NiS2O3·6H2O, light green columnar crystals. The purity of the product is between 94 and 96 percent. When the temperature is less than or equal to 10 ℃, the thermal stability is better, and the decomposition reaction can not occur. But the crystal water is lost to a different extent.
Detailed Description
A method for removing copper from nickel electrolyte by purification is characterized in that nickel thiosulfate is added into the nickel electrolyte as a copper removing agent for copper removal and purification, and the technological process comprises the following steps: in nickel electrolyte as S2O3 2-/Cu2+Adding nickel thiosulfate in a molar ratio of 4.4-7: 1, and adding acid to adjust the pH value at a temperature of 65-70 ℃: the PH value is 0.5-2; stirring and reacting time: and (3) separating and generating a CuS precipitate after 30-40min to obtain a purified copper-removed solution. The preparation process of the copper removing agent of the nickel thiosulfate comprises the following steps: according to BaS2O3And NiSO4The molar ratio of the components is 1: 0.94, and the reaction temperature is 35-40 ℃, and the reaction time is 90min, so that the liquid nickel thiosulfate copper remover is generated.
Example 1
Preparation method of nickel thiosulfate
Weighingappropriate amount of NiCO3It is placed in a sulfurous acid solution to be first converted into nickel sulfite, and then excess sulfur powder is added. Heating and refluxing for a certain time under the action of a catalyst, cooling to room temperature, filtering to remove residues, and collecting filtrate. The detection proves that the filtrate contains a certain concentration of thiosulfate ions. Repeating the experiment, and when the concentration fluctuation is between 0.5-1.8 moL, the direct yield is 50% -75% in terms of nickel.
Example 2
Preparation method of nickel thiosulfate
(1) Preparation of barium thiosulfate
Finding BaS by orthogonal experiment method2O3Optimum preparation conditions of
Reason for watchPlain level meter
| A | B | C | |
| Proportioning (mol/mol) | Temperature of | Time min | |
| 1 | 0.98∶1 | 20 | 5 |
| 2 | 1∶1 | 30 | 10 |
| 3 | 1∶0.98 | 40 | 15 |
Note: the ratio is Na2S2O3·5H2O and BaCl2·2H2Molar ratio of OFrom the analysis, scheme C2A2B1Is most preferred. Namely:
① the ratio is 1: 1
② temperature 20 deg.C (near room temperature)
③ stirring for 10min to obtain relatively pure BaS2O3Mixing BaS2O3And washing the mixture for 2-3 times by using hot water with the temperature of about T ≈ 60 ℃.
(2) Preparation of liquid nickel thiosulfate decoppering agent an orthogonal experiment was used to find the best preparation conditions for preparing liquid nickel thiosulfate decoppering agent
Level meter for two factors of table
| A | B | C | |
| Proportioning (mol/mol) | Reaction time min | Temperature of | |
| 1 | 1∶0.94 | 30 | 20 |
| 2 | 1∶1 | 60 | 30 |
| 3 | 0.94∶1 | 90 | 35 |
Note: the ratio is BaS2O3And NiSO4The molar ratio of (B) is known from analysis, scheme C3A1B3Is most preferred. Namely:
① the ratio is 1: 0.94
② temperature 35 deg.C (near room temperature)
③ reaction time 90min
c, for the preparation of the solid nickel thiosulfate decoppering agent, an orthogonal experiment is adopted to find the optimal preparation condition for preparing the liquid nickel thiosulfate decoppering agent
Horizontal meter with three factors
| A | B | C | |
| Proportioning (ml/ml) | Time h | Concentration of liquid nickel thiosulfate decoppering agent (i.e., S)2O3 2-Content of) g/L | |
| 1 | 1∶2.5 | 16 | 80 |
| 2 | 1∶3.5 | 24 | 120 |
| 3 | 1∶4.5 | 32 | 160 |
Note: the proportioning refers to the volume ratio of the liquid nickel thiosulfate decoppering agent to the concentrating agent, and the reaction time refers to the standing time of crystallization
Note: in order to examine the problem of recovery, the oxidized part of the crystals was recovered, and thus the purity was affected to some extent.
From the analysis, scheme C1A3B2Is most preferred. Namely:
① the ratio is 1: 4.5
② crystallization time 24h
③ concentration of liquid nickel thiosulfate decoppering agent (i.e. S)2O3 2-Content of) 80g/L
In the series of crystallization and concentration processes, the concentration of a liquid sample is found to have a certain relation with the purity of the prepared solid product. Specifically, the lower the concentration of the liquid nickel thiosulfate copper removing agent is, the higher the purity of the prepared solid is.
Example 3
Firstly, regulating the value of the iron liquid to a preset value by using sulfuric acid, measuring the solution, putting the solution in a beaker, and putting the beaker in an electronic temperature-controlled water bath kettle. And the temperature adjusting controller is preset to a preset temperature, and the stirring is slowly carried out while the temperature is increased. When the temperature of the solution reaches a preset value, adding a proper amount, starting timing, filtering the solution after the reaction is finished, and analyzing the components of the filtrate and the slag.
The copper removing exploratory test of the nickel thiosulfate copper removing agent has the copper removing conditions as follows: the reaction temperature is 60 ℃, the reaction time is 15min, the pH value of the solution is controlled between 3.5 and 4.0, the volume of the solution after iron removal is 600ml, and 38ml of liquid nickel thiosulfate decoppering agent (containing S) is added2O3 2-120g/l) of [ S]2O3 2-]∶[Cu2+](MR)＝7∶1，
The experimental results are now tabulated as follows:
table four experimental results table
| Component (A) | Ni(g/l) | SO4 2-(g/l) | S2O3 2-(g/l)- | Cu(g/l) | PH |
| Copper removal precursor solution | 71.8 | 111.52 | 0.60 | 3.8 | |
| Liquid after copper removal | 72.75 | 120.02 | 7.68 | 0.54 | 4.0 |
Condition test
From the above experimental results, it is clear that the copper removal effect under the above conditions is not ideal, the copper content of the solution is reduced by 0.06g/l, and the S content in the solution is reduced2O3 2-The total amount of S added2O3 2-The change is very slight, that is to say, under the reaction condition, the added copper removing agent hardly takes part in the reaction and is not decomposed. Therefore, it is difficult to achieve a predetermined copper removal effect without changing the reaction conditions, and the corresponding copper removal conditions are changed as follows:
a. experiment of influence of temperature on copper removal effect
The copper removal pre-liquid comprises the following components: ni: 77.44g/l, Cu: 0.60g/l, Co: 0.28g/l, SO4 2-: 111.89g/l, other conditions and test results are given in the following table:
TABLE V influence of temperature on copper removal
| Reaction temperature (℃) | Time of day (min) | PH | Copper rear liquid component (g/l) | |||
| Before copper removal | After copper removal | Cu | SO4 2- | S2O3 2- | ||
| 70 | 30 | 3.6 | 3.0 | 0.26 | 120 | 6.45 |
| 80 | 30 | 3.7 | 2.8 | 0.15 | 121 | 6.23 |
| 86 | 30 | 3.7 | 2.6 | 0.11 | 120.2 | 6.22 |
| 90 | 30 | 3.6 | 2.5 | 0.010 | 4.76 | |
| 96 | 30 | 3.6 | 2.4 | 0.0004 | 4.15 | |
From the above test results, it can be seen that the reaction temperature has a great influence on the copper removal depth, and it can be seen that under the same conditions, the copper content of the solution gradually decreases with the increase of the reaction temperature, which indicates that the increase of the temperature is beneficial to the copper removal reaction. The temperature has a very obvious influence on the copper removal depth, and the reaction temperature is a very critical factor.
b. Influence of solution pH on copper removal
Tests have found that when the pH of the solution before copper removal is greater than 2.0, the copper removal depth is difficult to reachbelow 0.002g/l even if the nickel thiosulfate copper remover is added to the solution in a molar ratio of 7: 1. Other conditions and test results are shown in the following table:
influence of pH value of solution to decoppering effect
| Temperature (. degree.C.) | pH value | Addition amount (MR) | Time (min) | Liquid after copper removal (Cu)2+g/l) |
| 70 | 1.2 | 7∶1 | 15 | 0.0005 |
| 70 | 1.5 | 7∶1 | 15 | 0.002 |
| 70 | 2.0 | 7∶1 | 15 | 0.033 |
| 70 | 2.5 | 7∶1 | 15 | 0.22 |
It can be seen that, under the same conditions, the influence of the solution PH on the copper removal effect is more obvious, the lower the solution PH is, the better the copper removal effect is, and when the PH is greater than 2, the stronger the influence degree is, i.e. the copper removal effect is poor, and when the PH is less than 2, as the PH is reduced, the better the copper removal effect is, which indicates that the PH equal to 2 is a critical point for copper removal under the conditions.
c. Effect of reagent addition on copper removal depth
The adding amount of the nickel thiosulfate copper removing agent also has certain influence on the copper removing depth, and the specific table is as follows:
influence of the amount of the reagent added to the copper removal
| Temperature (. degree.C.) | Addition amount (MR) | pH value | Time (min) | Liquid after copper removal (Cu)2+g/l) |
| 70 | 15 | 2.0 | 30 | 0.14 |
| 70 | 20 | 2.0 | 30 | 0.001 |
| 70 | 25 | 2.0 | 30 | 0.0005 |
| 70 | 30 | 2.0 | 30 | 0.0004 |
As can be seen from the above table, under the same conditions, the larger the reagent addition, the better the copper removal effect, and the lower the copper content of the solution after copper removal. Meanwhile, tests show that the reagent dosage can be reduced by increasing the reaction temperature under certain other conditions, and the same copper removal depth can be achieved by increasing the reagent dosage when the reaction temperature is reduced.
d. Effect of time on copper removal
In general, the longer the reaction time, the more complete the reaction. This test also demonstrates this. From the data in the table below, it can be seen that under the same conditions, the copper content of the copper-removed solution gradually decreases with time, but the influence degree is not too great.
TABLE eight Effect of time on copper removal
| Temperature (. degree.C.) | Time (min) | Addition amount (MR) | pH value | Liquid after copper removal (Cu)2+g/l) |
| 70 | 15 | 20 | 2.0 | 0.063 |
| 70 | 20 | 20 | 2.0 | 0.012 |
| 70 | 30 | 20 | 2.0 | 0.001 |
Example 4
Confirmatory experiment
According to the four conditions influencing the copper removal effect, the condition closest to the existing production is selected for verification experiment.
The specific conditions are as follows: temperature: 65-70 ℃; reacting for 30 min; pH value of the solution: the PH value is less than or equal to 2; the dosage of the copper removing agent of the nickel thiosulfate is as follows: s2O3 2-/Cu2+(MR)>4.4; stirring speed: 200 to 250r/min
Therefore, the following steps are carried out: tests are carried out under the conditions, the copper removal effect is very satisfactory, the copper content of the copper removal solution is almost less than 0.001g/l, the nickel content of the copper slag is extremely low, and the copper-nickel ratio reaches more than 100: 1. The method is the best condition suitable for the current production process, the existing copper removing equipment for production can be used for production without great change, and the copper removing requirement of the first-grade electrolytic nickel can be met.
The copper removal by the nickel thiosulfate decoppering agent is used for copper removal by a nickel electrolysis cleaning solution, the technical conditions are loose, and the operation is easy for workers. The copper-nickel ratio in the copper slag after copper removal is far more than 20: 1, the nickel content in the slag is less than 1%, the copper slag can completely enter a copper system as copper concentrate, an open circuit of copper is formed, the circulation of copper in nickel electrolysis is not caused, the recovery rate and the direct recovery rate of nickel are improved, other harmful ions cannot be brought into a solution system by the method, and S which does not completely react is not generated2O3 2-The stability of the ions is poor, and the ions are easily oxidized into sulfate ions by chlorine when entering the next cobalt removal process, so that the method does not bring adverse effects to the next electrolysis process. The method adopts the copper removing agent of the nickel thiosulfate, and the production raw materials are new liquid of a nickel electrolysis system or solution containing the nickel sulfate, partial solid nickel sulfate, S powder and SO2Is a byproduct of nickel-cobalt metal, and the raw material source is convenient. The copper removing agent for nickel thiosulfate is produced by using new electrolytic solution, in which nickel is only used as carrier of nickel thiosulfate in the whole process, and when the copper is removed, it can be returned into nickel electrolytic system, and its Ni content can be raised2+The concentration is 2-4 percentage points, and no loss is caused.
The thiosulfate decoppering agent is easy to dissolve in water, and the nickel content in the copper slag can not be increased even if the thiosulfate decoppering agent is added excessively during decoppering, which is different from decoppering of nickel powder, nickel concentrate and nickel sulfide, so that the nickel content in the slag is low. The use of the copper removing agent of the nickel thiosulfate reduces the amount of copper slag to 1/4 at present, reduces the process intensity and saves manpower and energy consumption.
Claims (4)
1. A method for removing copper from nickel electrolyte is characterized in that nickel thiosulfate is added into the nickel electrolyte as a copper removing agent for copper removal and purification, and the technical process is as follows: in nickel electrolyte as S2O3 2-/Cu2+Adding nickel thiosulfate in a molar ratio of 4.4-7: 1, and adding acid at 65-70 ℃ to adjust the pH value to 0.5-2; stirring for reaction for 30-40min, and filtering to separate out the generated CuS precipitate to obtain the copper-removed solution.
2. The method for purifying and decoppering nickel electrolyte according to claim 1, wherein the preparation process of adding the nickel thiosulfate decoppering agent into the nickel electrolyte comprises: according to BaS2O3And NiSO4The molar ratio of the components is 1: 0.94, the reaction temperature is 35-40 ℃, the reaction time is 85-110min,
to prepare the liquid nickel thiosulfate copper remover.
3. The method for purifying and decoppering nickel electrolyte according to claim 1, wherein in the preparation process of adding the copper thiosulfate into the nickel electrolyte solution, the prepared liquid copper thiosulfate is added with the ethanol as the concentrating agent according to the ratio of 1: 2.5-4.5, and the reaction time is 24 hours, so as to prepare the solid copper thiosulfate.
4. The method as claimed in claim 1, wherein the concentration of ethanol is added to the liquid nickel thiosulfate with a concentration of 80-160 g/L.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100568942A CN100378233C (en) | 2004-08-30 | 2004-08-30 | Process for cleaning decopper nickel electrolytic solution |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100568942A CN100378233C (en) | 2004-08-30 | 2004-08-30 | Process for cleaning decopper nickel electrolytic solution |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1598012A true CN1598012A (en) | 2005-03-23 |
| CN100378233C CN100378233C (en) | 2008-04-02 |
Family
ID=34666219
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2004100568942A Expired - Fee Related CN100378233C (en) | 2004-08-30 | 2004-08-30 | Process for cleaning decopper nickel electrolytic solution |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100378233C (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101063210B (en) * | 2006-04-25 | 2010-05-26 | 襄樊化通化工有限责任公司 | Technique for producing high activity nickel cake with regeneration of waste material containing nickle as raw material |
| CN103320622A (en) * | 2013-07-18 | 2013-09-25 | 海南金亿新材料股份有限公司 | Technological process for preparing electronic-grade nickel methylsulfonate by utilization of nickel waste material |
| CN103320811A (en) * | 2013-06-05 | 2013-09-25 | 中南大学 | Method for removing impurities from nickel electrolysis anolyte |
| CN103820809A (en) * | 2014-02-28 | 2014-05-28 | 金川集团股份有限公司 | Copper removal method |
| CN106834740A (en) * | 2016-12-30 | 2017-06-13 | 四川师范大学 | The method for decoppering of nickel solution |
| CN115650319A (en) * | 2022-10-22 | 2023-01-31 | 兰州大学 | Method for synchronously and efficiently removing copper ions and cobalt ions from nickel sulfate solution |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU1827393C (en) * | 1991-04-17 | 1993-07-15 | Химико-металлургический институт АН КазССР | Method of copper precipitation from copper-nickel sulfate electrolyte |
| CN1088266A (en) * | 1993-12-27 | 1994-06-22 | 杨春青 | The method and apparatus of leaching and recoverying copper, silver, gold, lead, iron, sulphur from sulphuretted copper ore |
| CN1032703C (en) * | 1994-06-29 | 1996-09-04 | 北京有色冶金设计研究总院 | Method for removal of copper from electrolytic nickel anodic liquid |
| CA2237710C (en) * | 1998-05-14 | 2002-07-30 | Falconbridge Limited | Recovery of nickel from copper refinery tankhouse electrolyte |
-
2004
- 2004-08-30 CN CNB2004100568942A patent/CN100378233C/en not_active Expired - Fee Related
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101063210B (en) * | 2006-04-25 | 2010-05-26 | 襄樊化通化工有限责任公司 | Technique for producing high activity nickel cake with regeneration of waste material containing nickle as raw material |
| CN103320811A (en) * | 2013-06-05 | 2013-09-25 | 中南大学 | Method for removing impurities from nickel electrolysis anolyte |
| CN103320811B (en) * | 2013-06-05 | 2015-08-12 | 中南大学 | A kind of method removing impurity from nickle electrolysis anode solution |
| CN103320622A (en) * | 2013-07-18 | 2013-09-25 | 海南金亿新材料股份有限公司 | Technological process for preparing electronic-grade nickel methylsulfonate by utilization of nickel waste material |
| CN103820809A (en) * | 2014-02-28 | 2014-05-28 | 金川集团股份有限公司 | Copper removal method |
| CN103820809B (en) * | 2014-02-28 | 2017-03-01 | 金川集团股份有限公司 | A kind of copper-removing method |
| CN106834740A (en) * | 2016-12-30 | 2017-06-13 | 四川师范大学 | The method for decoppering of nickel solution |
| CN106834740B (en) * | 2016-12-30 | 2019-02-12 | 四川师范大学 | The method for decoppering of nickel solution |
| CN115650319A (en) * | 2022-10-22 | 2023-01-31 | 兰州大学 | Method for synchronously and efficiently removing copper ions and cobalt ions from nickel sulfate solution |
| CN115650319B (en) * | 2022-10-22 | 2024-02-20 | 兰州大学 | Method for synchronously and efficiently removing copper and cobalt ions from nickel sulfate solution |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100378233C (en) | 2008-04-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1055971C (en) | Chloride assisted hydrometallurgical extraction of nickel and cobalt from sulfide minerals | |
| CN102912138B (en) | Method of recycling zinc, manganese, lead and silver from zinc electrowinning anode mud | |
| CN1377980A (en) | Process for preparing high purity ammonium para-tungstate using hihg-molybdenum tungsten ore | |
| CN1243838C (en) | Technology for preparing cell-level high purified nickel sulfate by the selective leach of water quenching high grade nickel and sulfuric acid | |
| CN1295355C (en) | Method of manufacturing electrolytic metal manganese using titanium white waste acid and manganese dioxide ore | |
| CN112717468A (en) | Method for recovering lithium in lithium precipitation mother liquor | |
| CN104419826B (en) | The method that ammonia soaks Zinc Oxide electrowinning zinc | |
| CN109809440B (en) | Method for preparing high-purity lithium chloride, high-purity lithium formate and high-purity lithium carbonate | |
| CN1008118B (en) | Prepn. of znso4 and active zno from zinc ore by entire wet-process | |
| CN108517538B (en) | The method of waste solution of copper electrolysis synthetical recovery processing | |
| CN1598012A (en) | Process for cleaning decopper nickel electrolytic solution | |
| CN101838750A (en) | Method for performing direct acid adjusting closed cycle on ammonium paratungstate crystallization mother liquor | |
| CN112725621B (en) | Method for separating nickel, cobalt and manganese from waste lithium battery based on carbonate solid-phase conversion method | |
| CN101134566B (en) | Process for preparing amino-sulfonic acid nickel by nickel sulfide concentrate | |
| CN101260539A (en) | Purifying and impurity-removing method for copper electrolytic solution | |
| CN102851508B (en) | Method for producing electrolytic lead powder through alkali immersion rotational flow electrolysis of wet electrolytic zinc acid dipping residues | |
| CN107419301A (en) | A kind of preparation method of complex precipitant and a kind of purification method of copper electrolyte | |
| CN109534369B (en) | Membrane integrated lithium chloride preparation equipment and method thereof | |
| CN1172074A (en) | Preparation method of cupric oxide or cupric sulfate using copper sheathed steel by ammonia immersion | |
| CN1598013A (en) | Process for removing copper of cobalt electrolytic solution | |
| CN108069851A (en) | A kind of method that no ammonia oxalic acid precipitation prepares cobalt oxalate | |
| CN108428893A (en) | Preparation method of brine battery-grade lithium carbonate | |
| CN102888624A (en) | Method for producing superfine zinc powder by performing cyclone electrolyzing on zinc-containing alkali liquor | |
| CN1018660B (en) | Production process of fibrous electrolytic manganese dioxide and special electrolytic bath device | |
| CN116216749B (en) | Method for preparing battery grade lithium carbonate by using salt lake lithium carbonate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C56 | Change in the name or address of the patentee |
Owner name: JINCHUAN GROUP CO., LTD. Free format text: FORMER NAME: JINCHUAN GROUP CORP., LTD. |
|
| CP01 | Change in the name or title of a patent holder |
Address after: 737103 Jinchang City, Gansu province Jinchuan Group Ltd Patentee after: JINCHUAN GROUP Co.,Ltd. Address before: 737103 Jinchang City, Gansu province Jinchuan Group Ltd Patentee before: Jinchuan Group Co.,Ltd. |
|
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20080402 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |