CN1115338A - Method for removing copper from Ni or Co acid solution - Google Patents
Method for removing copper from Ni or Co acid solution Download PDFInfo
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- CN1115338A CN1115338A CN94108441A CN94108441A CN1115338A CN 1115338 A CN1115338 A CN 1115338A CN 94108441 A CN94108441 A CN 94108441A CN 94108441 A CN94108441 A CN 94108441A CN 1115338 A CN1115338 A CN 1115338A
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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
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract
The process for removing Cu from acidic solution of Ni or Co includes adding and suspending the sulfur flour pretreated with wetting agent in original solution, and blowing-in SO2 gas under a certain temp., pressure and pH value of solution to crystallize copper sulfide, and features coarse crystallized Cu particles with good settling and filter performance, low Ni and Co contents, quick Cu-removing speed, no pollution to original solution and stable quality of product.
Description
The present invention relates to a method for removing copper from an acidic solution of nickel or cobalt.
Due to the development of nickel and cobalt chlorination metallurgy technology and the approach of the quality of nickel and cobalt products to international standards, the research on how to remove copper from nickel and cobalt liquid containing or not containing chloride radical becomes necessary and urgent, and a new economic and effective copper removal method without polluting the original liquid and products is needed.
The existing copper removal methods, such as a sulfuration method, a replacement method, an extraction method, an ion exchange method and the like, are limited by economic, technical or geographical conditions, so that the requirements are difficult to meet. For example:
(1) and (3) a vulcanization method: various copper sulfide precipitating agents are used to sulfide copper. Wherein H2The S method is applied abroad, and can remove copper to 0.001g/l, and has the defect of H2The strong toxicity of S and the reasons of fine granularity of copper slag produced in the copper removing process, poor sedimentation and filtration performance, high Ni and Co contents and the like are not popularized and applied in China. Na (Na)2S and (NH)4)2The S method can introduce partial Na into the original liquid+、NH4 +And the high Ni and Co contents of the copper slag are not popularized and applied.
(2) Substitution method:
A. active nickel powder replacement method: the depth and rate of copper removal by nickel powder displacement are limited by the particle size and activity of the nickel powder. The difficulty of preparing, storing and transporting the active nickel powder, the high price and the high nickel content of the copper slag limit the application of the method, and are particularly not suitable for the factory use of a crude nickel anode-free electrolytic refining system and the undesirable off-site Ni2+And (4) removing copper from the cobalt solution introduced by the ions.
B. Nickel powder + sulfur powder method: in order to improve the activity of the nickel powder, sulfur powder is added into the copper removing liquid. The adaptability and existing problems of the method are the same as those of A.
C.Ni3S2+ S substitution method: at present, the method is generally adopted in China to remove copper from a copper-containing nickel solution. The main disadvantage of this method is that the produced copper slag contains up to 40% nickel and cannot be used for copper smeltingRaw materials; is not suitable for introducing Ni2+Copper removal of ionic cobalt solutions.
3. Extraction method and ion exchange method: is a copper removing method which replaces a slag process with a non-slag process. The disadvantages of the method are low reaction speed, small adsorption capacity, poor adaptability and the like, and the method is difficult to be widely used in large-scale production.
The invention aims to overcome the defects in the prior art and provide a copper removal method which can remove copper in an acidic nickel solution and can also remove copper in an acidic cobalt solution, and the crystallized copper slag has coarse particles, good sedimentation and filtration performances and low nickel and cobalt contents and does not introduce pollution ions into an original solution.
The object of the present invention can be achieved by the following means.
Adding sulfur powder which is pretreated by a wetting agent and is necessary for generating copper sulfide into nickel and cobaltic chloride solution or chloride-sulfate mixed solution or sulfate solution containing copper ions in stoichiometric or more, and blowing sulfur dioxide gas under the conditions of certain temperature, pressure and solution pH in a state that the sulfur powder is suspended, so that nickel and cobalt in the solution are not vulcanized and copper is vulcanized to generate crystalline copper sulfide.
The main copper removal reaction is as follows:
the main technical conditions and requirements of the present invention are as follows from the above reaction.
The nickel and cobalt solution to be decoppered can be a chloride solution, a chloride-sulfate mixed solution and a sulfate solution, and has no strict requirement on the contents of copper, nickel and cobalt in the solution. The copper removal process can be carried out in a wide range of the acidity of the original liquor.
The amount of sulfur powder added in the copper removing reaction is that the molar ratio of sulfur to copper is more than 1. The granularity of the sulfur powder is 0.147-0.053 mm, and the sulfur powder is pretreated by a wetting agent before reaction. The wetting agents are: gleditschia horrida water, sodium alkyl iodide, hexadecyl ammonium bromide and OT.
The reaction temperature for copper removal is higher than 50 ℃, and is generally controlled at 70-120 ℃.
Copper removal reaction total pressure is looked at Cl in solution-The content is determined by the copper removal depth. Low chlorine contentAt 60g/l, the copper removal reaction can be operated at normal pressure; when the chloride content is higher than 60g/l, copper is removedThe method is carried out under super-normal pressure, and the total pressure is required to be more than or equal to 0.103MPa and is generally controlled to be 0.103-0.30 MPa.
The copper removing reaction can be less than 100gH2SO4In the range of very large acidity,/l. For containing Cu2+When the pH value of the initial acidity of the solution is less than or equal to 1g/l and is 2-3, the copper can be deeply removed without adding a neutralizing agent to adjust the pH value in the reaction process, but for a high-copper solution, the neutralizing agent needs to be added in the reaction process to maintain the pH value of the reaction solution to be greater than 1. The neutralizer can be carbonate, hydroxide, sulfide or oxide of the main metal in the copper liquid, and other neutralizers can be used according to actual conditions.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention has no strict requirement on the contents of copper, nickel and cobalt in the original liquid, has wider acidity range and strong adaptability.
2. The copper removing effect is obvious, the produced copper sulfide slag has coarse crystal particles, good sedimentation and filtration performance, and low nickel and cobalt contents in the copper slag, and can be used as a raw material for copper smelting.
3. No toxicity, no pollution to the original liquid, high copper removing reaction speed and large capacity.
4. The produced cobalt and nickel products have stable quality, meet the national standard, have obvious economic benefit, and all technical indexes meet the national standard requirements.
The embodiment of the invention is as follows:
example 1: the test solution is a leaching solution obtained by pressurizing and oxygen leaching matte containing nickel, copper and cobalt in nickel production, and comprises the following components (g/l):
| Ni ～87 | Co ～3.9 | Cu ～23.90 | Fe ～2.84 | H+(mol/l) ～0.28 |
adjusting the pH value of the original liquid to 3.0, adjusting the reaction temperature to 80-90 ℃, adjusting the molar ratio of sulfur powder to copper to be 1.3: 1, adjusting the particle size of the sulfur powder to-0.074 mm, pretreating the sulfur powder by using a wetting agent before reaction, adding the pretreated sulfur powder into a liquid before copper removal, blowing sulfur dioxide gas into the liquid when the sulfur powder is in a suspension state, performing the copper removal process under the conditions of normal pressure and no addition of a neutralizing agent, and reacting for 2 hours to obtain the following results:
| liquid component (g/l) after copper removal | Copper slag (%) | ||||||||
| Ni | Co | Cu | Fe | H mol/L | Ni | Co | Cu | Fe | S |
| ～89.2 | ～3.9 | ～0.01 | ～3.0 | ～1.6 | ～0.14 | ～0.007 | ＞58 | ＜0.03 | ～38 |
Example 2: the solution used for the test is a cobalt slag leaching solution, and the copper is removed according to the copper removal method of the invention, so that the following results are obtained:
| before copper removalLiquid (g/l) | Liquid after copper removal (g/l) | Yield copper slag (%) | |||||||||
| Co | Ni | Cu | Fe | Co | Ni | Cu | Fe | Co | Ni | Cu | Fe |
| ～45.3 | ～3.1 | ～4.4 | 0.11 | 47.6 | 4.4 | ＜0.01 | 0.12 | ＜1 | ～0.3 | ～30 | Micro-meter |
Example 3: the test solution is electrolytic waste liquid obtained by nickel sulfide anode electrolysis, and the composition (g/l) of the test solution is as follows:
| Ni | Co | Cu | Fe | Na+ | pH | Cl- |
| ～70 | ～0.3 | ～0.62 | ～0.005 | ～38 | ～4.0 | ～64 |
adjusting the pH value of the original solution to 3.0, at the reaction temperature of 80 ℃, the molarratio of the sulfur powder to the copper is 1.5, the particle size of the sulfur powder is-0.074 mm, pretreating the sulfur powder by using OT solution before reaction, adding the pretreated sulfur powder into the solution before copper removal, blowing sulfur dioxide in the solution under the conditions that the sulfur powder is in a suspension state and the pressure of a reaction system is over normal pressure, not adjusting the pH value of the solution in the whole reaction process, and obtaining the following results after 2 hours:
| copper-removed liquid component (g/l) | Copper slag composition (%) | |||||
| Ni | Co | Cu | pH | Ni | Co | Cu |
| ～70.4 | ～0.3 | ＜0.001 | ～2.0 | ＜1.0 | ＜0.002 | ～40 |
Example 4: the test solution is a solution produced by chlorine leaching of a copper-nickel alloy, and the composition (g/l) of the test solution is as follows:
the copper removal is carried out according to the copper removal method of the invention, and the following results are obtained after 2 hours of reaction:
| Ni | Cu | Co | Fe |
| 180 | 50 | 4.5 | 22 |
| S/Cu molar ratio | Residual copper in solution (g/l) | Copper slag composition (%) | |||
| Cu | Ni | Co | Cu/Ni | ||
| 1.1 1.5 2.1 | 0.25 0.06 ＜0.03 | 56 53 42 | 0.15 0.17 0.27 | ＜0.01 ＜0.01 ＜0.01 | ～375 ～314 ～156 |
The invention has been applied to the copper removal in the nickel and cobalt production in China, for example, the invention has been applied to the industrial production of cobalt sulfate, and the controlled technical conditions are as follows:
temperature: -80 ℃ of temperature;
the dosage of the sulfur powder is as follows: -20 kg/ton product;
sulfur dioxide usage (at atmospheric pressure): 360 kg/ton product;
original liquid: the pH is 3-4, and the acidity does not need to be adjusted in the copper removing process;
copper removal effect: 60-80 g/l of Co and 0.3-0.5 g/l of Cu before copper removal,
pH3～4；
after copper removal, the Co content of the solution is 60-80 g/l, the Cu content is less than 0.003g/l,
pH2～3；
the copper slag contains Co: less than 0.5 percent;
the quality of the produced cobalt sulfate product is as follows: all reach the national standard.
After the invention is used, the quality of the cobalt sulfate product in the factory is very stable, the economic benefit is obvious, the annual profit and tax creation is more than 223 ten thousand yuan, and the accumulated profit and tax creation is more than 700 ten thousand yuan.
Claims (10)
1. A method for removing copper from a nickel or cobalt acidic solution, characterized by: taking a copper-containing nickel and cobaltic chloride solution or a chloride-sulfate mixed solution or a sulfate solution as an original solution; taking sulfur powder and sulfur dioxide gas as an oxidation-reduction agent; adding proper amount of sulfur powder pretreated by wetting agent, suspending the sulfur powder, blowing sulfur dioxide gas at certain temperature, pressure and pH value of the solution, adding neutralizing agent in the copper removing process, and carrying out copper sulfide deposition reaction to produce crystallized coarse-grained copper sulfide slag.
2. The method according to claim 1, characterized in that the virgin liquor has no special requirements for copper, nickel and cobalt contents.
3. A process according to claim 1, characterized in that the sulphur powder of the oxido-reducer is suspended in a copper-containing nickel, cobalt acidic solution, the molar ratio of elemental sulphur in the sulphur powder to copper in the solution being greater than 1, typically between 1.0 and 3.0.
4. A method according to claim 1, characterized in that the sulphur dioxide gas is blown into the copper-containing acidic nickel, cobalt solution in which the sulphur powder is suspended, in an amount which is greater than the stoichiometric amount, typically 1.0 to 1.5 times.
5. The method according to claim 1, wherein the temperature of the copper deposition reaction must be higher than 50 ℃, and is usually controlled to be 70-120 ℃.
6. The method according to claim 1, characterized in that the copper-containing nickel, cobaltic acid solution, when the chloride content is less than 60g/l, the copper removal reaction is operated at normal pressure; when the chloride content is higher than 60g/l, the copper removal reaction is carried out under super-normal pressure, and the total pressure is generally controlled to be 0.103-0.30 MPa.
7. The method as claimed in claim 1, wherein the added sulfur powder has a particle size of 0.147-0.053 mm, and is subjected to pre-wetting treatment before copper removal, and the wetting agent is selected from water of Gleditsia sinensis Lam, sodium alkylsulfonate, ammonium cetyl bromide, and OT.
8. The method of claim 1, wherein the copper removal reaction is carried outCan be less than 100gH2SO4The copper removal is carried out in a large acidity range, and when the copper content of the solution is below 1g/l and the pH value of the initial acidity of the solution is 2-3, the copper can be removed without adding a neutralizing agent.
9. The method according to claim 1, characterized in that the neutralizing agent added during copper removal is a carbonate, sulfide, hydroxide or oxide of the bulk ion in the copper liquid to be removed.
10. The method of claim 1, wherein the method is not only suitable for copper removal of various solutions in nickel and cobalt production systems, but also can be popularized and applied to copper removal of solutions in which the potential of main metal ions in other metal production solutions is more negative than that of copper ions.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94108441A CN1115338A (en) | 1994-07-18 | 1994-07-18 | Method for removing copper from Ni or Co acid solution |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94108441A CN1115338A (en) | 1994-07-18 | 1994-07-18 | Method for removing copper from Ni or Co acid solution |
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| Publication Number | Publication Date |
|---|---|
| CN1115338A true CN1115338A (en) | 1996-01-24 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN94108441A Pending CN1115338A (en) | 1994-07-18 | 1994-07-18 | Method for removing copper from Ni or Co acid solution |
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| CN (1) | CN1115338A (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1062022C (en) * | 1998-01-07 | 2001-02-14 | 四川铜镍有限责任公司成都电冶厂 | Method for removing copper from melted nickle and cobalt |
| CN1318619C (en) * | 2004-08-30 | 2007-05-30 | 金川集团有限公司 | Process for removing copper of cobalt electrolytic solution |
| CN105838884A (en) * | 2016-04-21 | 2016-08-10 | 西北矿冶研究院 | Method for removing nickel from cobalt sulfate solution |
| CN107614711A (en) * | 2015-05-29 | 2018-01-19 | 住友金属矿山株式会社 | The purification process of cobalt chloride solution |
| CN111065751A (en) * | 2017-10-23 | 2020-04-24 | 住友金属矿山株式会社 | Method for separating copper from nickel and cobalt |
| CN111411229A (en) * | 2020-04-29 | 2020-07-14 | 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 |
| US11718894B2 (en) | 2017-12-18 | 2023-08-08 | Sumitomo Metal Mining Co., Ltd. | Method for separating copper, and nickel and cobalt |
| US11959151B2 (en) | 2017-09-29 | 2024-04-16 | Sumitomo Metal Mining Co., Ltd. | Method for separating copper from nickel and cobalt |
| US12000018B2 (en) | 2017-10-23 | 2024-06-04 | Sumitomo Metal Mining Co., Ltd. | Method for separating copper from nickel and cobalt |
-
1994
- 1994-07-18 CN CN94108441A patent/CN1115338A/en active Pending
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1062022C (en) * | 1998-01-07 | 2001-02-14 | 四川铜镍有限责任公司成都电冶厂 | Method for removing copper from melted nickle and cobalt |
| CN1318619C (en) * | 2004-08-30 | 2007-05-30 | 金川集团有限公司 | Process for removing copper of cobalt electrolytic solution |
| CN107614711A (en) * | 2015-05-29 | 2018-01-19 | 住友金属矿山株式会社 | The purification process of cobalt chloride solution |
| CN105838884A (en) * | 2016-04-21 | 2016-08-10 | 西北矿冶研究院 | Method for removing nickel from cobalt sulfate solution |
| US11959151B2 (en) | 2017-09-29 | 2024-04-16 | Sumitomo Metal Mining Co., Ltd. | Method for separating copper from nickel and cobalt |
| CN111065751A (en) * | 2017-10-23 | 2020-04-24 | 住友金属矿山株式会社 | Method for separating copper from nickel and cobalt |
| CN111065751B (en) * | 2017-10-23 | 2021-03-23 | 住友金属矿山株式会社 | Method for separating copper from nickel and cobalt |
| US12000018B2 (en) | 2017-10-23 | 2024-06-04 | Sumitomo Metal Mining Co., Ltd. | Method for separating copper from nickel and cobalt |
| US11718894B2 (en) | 2017-12-18 | 2023-08-08 | Sumitomo Metal Mining Co., Ltd. | Method for separating copper, and nickel and cobalt |
| CN111411229A (en) * | 2020-04-29 | 2020-07-14 | 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 |
| 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 |
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