CN110423898B - Desiliconization method in laterite nickel ore leaching process - Google Patents
Desiliconization method in laterite nickel ore leaching process Download PDFInfo
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- CN110423898B CN110423898B CN201910797647.4A CN201910797647A CN110423898B CN 110423898 B CN110423898 B CN 110423898B CN 201910797647 A CN201910797647 A CN 201910797647A CN 110423898 B CN110423898 B CN 110423898B
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0407—Leaching processes
- C22B23/0415—Leaching processes with acids or salt solutions except ammonium salts solutions
- C22B23/043—Sulfurated acids or salts thereof
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0453—Treatment or purification of solutions, e.g. obtained by leaching
- C22B23/0461—Treatment or purification of solutions, e.g. obtained by leaching by chemical methods
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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
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Abstract
The invention provides a desiliconization method in the process of leaching laterite-nickel ore. The method comprises the following steps: crushing the nickel hydroxide cobalt cake, and adjusting the water content to 60-80 wt%; mixing the crushed nickel-cobalt hydroxide cake with 45-60% sulfuric acid, curing at 60-90 ℃ for 0.5-3 h to obtain cured slurry, and then supplementing water to fix the volume to the pH value of 1.5-2; adding a reducing agent into the cured slurry to carry out reduction reaction to obtain reduced slurry; and carrying out solid-liquid separation on the reduction slurry to obtain desiliconized leaching solution and silicon-containing slag. The method provided by the invention can be used for fully removing silicon in the nickel cobalt hydroxide cake and avoiding the influence of overhigh silicon content on the subsequent nickel cobalt extraction, and meanwhile, the method has the advantages of simple process, low cost and low energy consumption.
Description
Technical Field
The invention relates to the technical field of hydrometallurgy, in particular to a desiliconization method in a laterite-nickel ore leaching process.
Background
Nickel is an important nonferrous metal, is widely applied to industries such as stainless steel, high-temperature alloy, electroplating, chemical engineering and the like, and has an extremely important position in national economic development. With the rapid increase of the economy of China, the increase rate of nickel consumption reaches more than 25% every year in recent years, and the nickel consumption rate becomes the first major nickel consuming country in the world. 70 percent of world land nickel resources are laterite type nickel oxide ore, but at present, only 40 percent of the nickel produced in the world is from laterite nickel ore every year, and with the gradual exhaustion of nickel sulfide resources, the key point of nickel resource development is transferred to laterite nickel ore internationally. The southeast Asia countries near the south and north Return line of the equator have abundant nickel laterite resources, and the nickel laterite resources are characterized by more lean ores, less rich ores, low mining cost and large reserves, and become important sources of nickel resources in China at present.
The hydrometallurgical process has the advantages of high metal recovery rate, large treatment capacity, good selectivity, small pollution, low energy consumption and the like, and is suitable for treating low-grade ores, so that the hydrometallurgical method for treating the low-grade nickel laterite is the main direction for researching the metallurgical process of the low-grade nickel laterite in the future. However, the laterite-nickel ore has high soluble silicon content, when a leaching-extraction process is adopted, silicon dioxide in the laterite-nickel ore is dissolved out in the form of silicic acid, when the leaching liquor is extracted, the silicic acid in the liquor forms a large amount of interphase dirt, the interphase dirt can cause difficult extraction and back extraction phase separation to cause phase entrainment, the extraction production is disordered, and the production stop is caused when the extraction is serious. Therefore, silicon removal is the most difficult in the wet leaching process.
Disclosure of Invention
The invention mainly aims to provide a desiliconization method in the laterite-nickel ore leaching process, so as to solve the problem that in the prior art, the phase splitting in the extraction process is difficult due to the over-high silicon content in the laterite-nickel ore treatment process by adopting a leaching-extraction process.
In order to achieve the above object, according to one aspect of the present invention, there is provided a desiliconization method in a lateritic nickel ore leaching process, which includes the steps of: crushing the nickel hydroxide cobalt cake, and adjusting the water content to 60-80 wt%; mixing the crushed nickel-cobalt hydroxide cake with 45-60% sulfuric acid, curing at 60-90 ℃ for 0.5-3 h to obtain cured slurry, and then supplementing water to fix the volume to the pH value of 1.5-2; adding a reducing agent into the cured slurry to carry out reduction reaction to obtain reduced slurry; and carrying out solid-liquid separation on the reduction slurry to obtain desiliconized leaching solution and silicon-containing slag.
Further, 0.5-2 ml of sulfuric acid is correspondingly added into each gram of the nickel cobalt hydroxide biscuit mine.
Further, crushing the nickel cobalt hydroxide cake to a granularity of 10-20 mm, and then performing a curing process.
Further, the desilication method comprises the following steps: crushing the nickel cobalt hydroxide cake to a particle size of 10-15 mm, and adjusting the water content to 60-65%; mixing the crushed nickel cobalt hydroxide cake with sulfuric acid with the mass concentration of 45-55%, wherein 0.8-1.5 ml of sulfuric acid is correspondingly added into each gram of nickel cobalt hydroxide biscuit ore, then curing for 1-2.5 h at the temperature of 80-90 ℃ to obtain cured slurry, and then supplementing water to fix the volume to 1.5-2; adding a reducing agent into the cured slurry to carry out reduction reaction to obtain reduced slurry; and carrying out solid-liquid separation on the reduction slurry to obtain desiliconized leaching solution and silicon-containing slag.
Further, the reducing agent is one or more of sodium metabisulfite, hydrogen peroxide, sodium sulfite and glucose.
Furthermore, the time of the reduction reaction is 0.5-1 h.
Furthermore, the addition amount of the reducing agent relative to the cured slurry is 5-15 wt%.
Furthermore, the solid-liquid separation process adopts a filter press filtration mode.
The nickel cobalt hydroxide cake is an intermediate product for leaching nickel and cobalt from the laterite nickel ore and is also a semi-finished product for leaching-extracting to produce nickel and cobalt, and the influence of the over-high silicon content on the production of the nickel cobalt hydroxide cake from the laterite nickel ore is small, but the influence on the later-stage working procedure for producing nickel and cobalt from the semi-finished product of the nickel cobalt hydroxide cake is larger. According to the invention, by controlling the water content of the nickel cobalt hydroxide cake, the crushed nickel cobalt hydroxide cake material with a specific water content is mixed with sulfuric acid with a specific mass concentration, and the mixture is cured under a specific reaction condition, so that nickel and cobalt in the nickel cobalt hydroxide cake can be leached into a liquid phase, meanwhile, leaching of silicon in the nickel cobalt hydroxide cake is inhibited, and silicon is separated out and added into slag. Then, reducing agent is added into the aged slurry for reduction reaction, so that manganese in the slag can be reduced into a liquid phase, and the separation of nickel, cobalt and manganese from the silicon slag is realized. In a word, the method provided by the invention can be used for fully removing silicon in the nickel cobalt hydroxide cake, and avoiding the influence of overhigh silicon content on the subsequent nickel cobalt extraction.
Detailed Description
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail with reference to examples.
As described in the background section of the present invention, the problem of difficult phase separation in the extraction process due to the excessive silicon content in the process of processing laterite-nickel ore by leaching-extraction process in the prior art exists. In order to solve the problem, the invention provides a desiliconization method in a laterite-nickel ore leaching process, which comprises the following steps: crushing the nickel hydroxide cobalt cake, and adjusting the water content to 60-80 wt%; mixing the crushed nickel-cobalt hydroxide cake with 45-60% sulfuric acid, curing at 60-90 ℃ for 0.5-3 h to obtain cured slurry, and then supplementing water to a constant volume of 1.5-2; adding a reducing agent into the cured slurry to carry out reduction reaction to obtain reduced slurry; and carrying out solid-liquid separation on the reduction slurry to obtain desiliconized leaching solution and silicon-containing slag.
In the leaching process, H is added to silicon in a dilute acid solution with the pH of 1-24SiO4And H5SiO4 +The reaction product can be reacted with hydroxyl to generate disilicic acid with the coordination number of silicate radical of 6, then polysilicic acid such as trisilicic acid is generated, and finally SiO is formed by polymerization2The sol is represented by the reaction formula (1). In SiO2In the sol, silicic acid continues to polymerize, gelation occurs to form gel, and part of water is trapped inside the gel as shown by the product structure in formula (1). The condition test has concluded that the gelation needs time and is closely related to pH or acidity, the silicic acid polymerization reaction rate is fast in an acidic solution with a larger pH value, and the occurrence of gelation will worsen the leaching and solid-liquid separation of other valuable elements in the laterite-nickel ore.
The nickel cobalt hydroxide cake is an intermediate product for leaching nickel and cobalt from the laterite nickel ore and is also a semi-finished product for leaching-extracting to produce nickel and cobalt, and the influence of the over-high silicon content on the production of the nickel cobalt hydroxide cake from the laterite nickel ore is small, but the influence on the later-stage working procedure for producing nickel and cobalt from the semi-finished product of the nickel cobalt hydroxide cake is larger. According to the invention, by controlling the water content of the nickel cobalt hydroxide cake, the crushed nickel cobalt hydroxide cake material with a specific water content is mixed with sulfuric acid with a specific mass concentration, and the mixture is cured under a specific reaction condition, so that nickel and cobalt in the nickel cobalt hydroxide cake can be leached into a liquid phase, meanwhile, leaching of silicon in the nickel cobalt hydroxide cake is inhibited, and silicon is separated out and added into slag. Then, reducing agent is added into the aged slurry for reduction reaction, so that manganese in the slag can be reduced into a liquid phase, and the separation of nickel, cobalt and manganese from the silicon slag is realized. In a word, the method provided by the invention can be used for fully removing silicon in the nickel cobalt hydroxide cake, and avoiding the influence of overhigh silicon content on the subsequent nickel cobalt extraction.
It should be noted here that the water is supplemented to a constant volume until the pH is 1.5-2, on one hand, the requirement in the nickel-cobalt process in the later extraction process is met, and on the other hand, the judgment on the concentration value of the silicon content is more effective on the premise of the same pH value condition. By utilizing the desiliconization method provided by the invention, the silicon content in the desiliconized leaching solution can be reduced to below 90ppm, most of the silicon content can be reduced to below 80ppm, and even reduced to below 50 ppm.
In a preferred embodiment, 0.5-2 ml of sulfuric acid is added to each gram of the cobalt-nickel hydroxide biscuit ore. Therefore, nickel cobalt and silicon can be more fully separated, so that leaching liquid of nickel cobalt element is fully performed, and the degree of separating silicon out and entering slag is improved. More preferably, in the crushing step, the nickel cobalt hydroxide cake is crushed to a particle size of 10 to 20mm and then subjected to the aging step, in order to sufficiently cure the nickel cobalt hydroxide cake.
In order to further enhance the desiliconization effect, in a preferred embodiment, the above desiliconization method comprises the steps of: crushing the nickel cobalt hydroxide cake to a particle size of 10-15 mm, and adjusting the water content to 60-65%; mixing the crushed nickel cobalt hydroxide cake with sulfuric acid with the mass concentration of 45-55%, wherein 0.8-1.5 ml of sulfuric acid is correspondingly added into each gram of nickel cobalt hydroxide biscuit ore, then curing for 1-2 hours at the temperature of 80-90 ℃ to obtain cured slurry, and then supplementing water to fix the volume to pH1.5-2; adding a reducing agent into the cured slurry with constant volume to carry out reduction reaction to obtain reduced slurry; and carrying out solid-liquid separation on the reduction slurry to obtain desiliconized leaching solution and silicon-containing slag.
In the desiliconization method, after the aged slurry is obtained, the manganese element in the slag can be reduced and leached into a liquid phase by adding a reducing agent to carry out a reduction reaction. In order to reduce the manganese element more sufficiently, in a preferred embodiment, the reducing agent is one or more of sodium metabisulfite, hydrogen peroxide, sodium sulfite and the like. More preferably, the time of the reduction reaction is 0.5 to 1 hour. Further preferably, the amount of the reducing agent added is 5 to 15wt% with respect to the aged slurry.
The solid-liquid separation process can adopt a common mode for treating solid-liquid slurry, and in a preferred embodiment, the solid-liquid separation process adopts a mode of filtering by a filter press. The mode is efficient and the separation effect is good.
In a word, the method provided by the invention can effectively remove silicon in the nickel hydroxide cobalt cake of the laterite-nickel ore semi-finished product, avoids influencing the subsequent extraction process of the leachate, and can reduce the silicon content in the leachate to 90ppm, and mostly to below 80ppm or even below 50 ppm. The method has simple process, low cost and low energy consumption, and is particularly suitable for wide application because the method can be directly arranged in the process of producing nickel and cobalt by leaching laterite nickel ore.
The present application is described in further detail below with reference to specific examples, which should not be construed as limiting the scope of the invention as claimed.
Example 1
Weighing 500g of a semi-finished product nickel cobalt hydroxide cake of laterite nickel ore with water content of 60 wt%, crushing the nickel cobalt hydroxide cake to a granularity of l0mm and 200ml of sulfuric acid with mass concentration of 46% (adding 100ml of water and then 100ml of concentrated sulfuric acid with mass concentration of 93%); curing the system at 80 ℃ for 1h, reacting silicon in the ore with sulfuric acid to generate silicon dioxide which is precipitated into slag, allowing nickel and cobalt to enter a liquid phase to form cured slurry, and then supplementing water to fix the volume to pH1.5;
adding a reducing agent sodium pyrosulfite into the aged slurry for reduction, wherein the adding amount of the reducing agent is 5wt%, and reacting for 0.5h to obtain reduced slurry;
and filtering the reduction slurry in a filter press to obtain the leachate with silicon removed.
And then, measuring the content of silicon in the leachate, wherein the content of silicon ions in the leachate can be less than 50 ppm.
Example 2
The difference from example 1 is that: the curing time is 0.5 h.
Then, the content of silicon ions in the leachate was measured to find that the content of silicon ions in the leachate was 75 ppm.
Example 3
The difference from example 1 is that: the curing time is 3 h.
Then, the content of silicon ions in the leachate was measured, whereby the content of silicon ions in the leachate was found to be 42 ppm.
Example 4
The difference from example 1 is that: the curing time is 2 h.
Then, the content of silicon ions in the leachate was measured to find that the content of silicon ions in the leachate was 45 ppm.
Example 5
The difference from example 1 is that: the sulfuric acid concentration was 60%.
Then, the content of silicon ions in the leachate was measured, whereby the content of silicon ions in the leachate was found to be 80 ppm.
Example 6
The difference from example 1 is that: the sulfuric acid concentration was 45%.
Then, measuring the content of silicon in the leachate to show that the content of silicon ions in the leachate is less than 50 ppm; .
Example 7
The difference from example 1 is that: the sulfuric acid concentration was 55%.
Then, the content of silicon ions in the leachate was measured to find that the content of silicon ions in the leachate was 67 ppm.
Example 8
The difference from example 1 is that: the curing temperature was 90 ℃.
Then, the content of silicon ions in the leachate was measured, whereby the content of silicon ions in the leachate was found to be 44 ppm.
Example 9
The difference from example 1 is that: the curing temperature was 60 ℃.
Then, the content of silicon ions in the leachate was measured, whereby the content of silicon ions in the leachate was found to be 88 ppm.
Example 10
The difference from example 1 is that: controlling the water content of the nickel hydroxide cobalt cake and the crushed material to be 80 wt%.
Then, the content of silicon ions in the leachate was measured, whereby the content of silicon ions in the leachate was found to be 62 ppm.
Example 11
The difference from example 1 is that: controlling the water content of the nickel hydroxide cobalt cake and the crushed material to be 65 wt%.
Then, the content of silicon ions in the leachate was measured, whereby the content of silicon ions in the leachate was found to be 52 ppm.
Example 12
The difference from example 1 is that: the crushing size is about 20 mm.
Then, the content of silicon ions in the leachate was measured, whereby the content of silicon ions in the leachate was found to be 49 ppm.
Example 13
The difference from example 1 is that: the particle size of the crushed particles is about 25 mm.
Then, the content of silicon ions in the leachate was measured, whereby the content of silicon ions in the leachate was found to be 52 ppm. However, the particles are too large to facilitate stirring during the curing reaction, and the stirring paddle is easy to damage.
Example 14
The difference from the embodiment 1 is that: the reducing agent is hydrogen peroxide.
Then, by measuring the content of silicon in the leachate, the content of silicon ions in the leachate is 47 ppm; .
Comparative example 1
The difference from the embodiment 1 is that: the aging time is 5 min.
Then, the content of silicon ions in the leachate was measured, and it was found that the content of silicon ions in the leachate was 120 ppm.
Comparative example 2
The difference from example 1 is that: the aging time is 10 min.
Then, the content of silicon ions in the leachate was measured, whereby the content of silicon ions in the leachate was found to be 117 ppm.
Comparative example 3
The difference from example 1 is that: the aging time is 20 min.
Then, the content of silicon ions in the leachate was measured, and it was found that the content of silicon ions in the leachate was 108 ppm.
Comparative example 4
The difference from the embodiment 1 is that: controlling the water content of the nickel hydroxide cobalt cake and the crushed material to be 58 wt%.
Then, the content of silicon ions in the leachate was measured, whereby the content of silicon ions in the leachate was found to be 101 ppm.
Comparative example 5
The difference from the embodiment 1 is that: controlling the water content of the nickel hydroxide cobalt cake and the crushed material to be 95 wt%.
Then, the content of silicon ions in the leachate was measured, whereby the content of silicon ions in the leachate was found to be 110 ppm.
Comparative example 6
The difference from the embodiment 1 is that: the curing temperature was 45 ℃.
Then, the content of silicon ions in the leachate was measured, whereby the content of silicon ions in the leachate was found to be 114 ppm.
Comparative example 7
The difference from example 1 is that: the curing temperature was 50 ℃.
Then, the content of silicon ions in the leachate was measured, whereby the content of silicon ions in the leachate was found to be 117 ppm.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (5)
1. A desiliconization method in a laterite-nickel ore leaching process is characterized by comprising the following steps:
crushing the nickel hydroxide cobalt cake, and adjusting the water content to 60-80 wt%;
mixing the crushed nickel-cobalt hydroxide cake with 45-60% sulfuric acid, curing at 60-90 ℃ for 0.5-3 h to obtain cured slurry, and then supplementing water to fix the volume to the pH value of 1.5-2; 0.5-2 ml of sulfuric acid is correspondingly added into each gram of the nickel cobalt hydroxide biscuit mine;
adding a reducing agent into the cured slurry to carry out reduction reaction to obtain reduced slurry; the reducing agent is one or more of sodium metabisulfite, hydrogen peroxide and glucose; the addition amount of the reducing agent relative to the cured slurry is 5-15 wt%;
and carrying out solid-liquid separation on the reduction slurry to obtain desiliconized leaching solution and silicon-containing slag.
2. The desiliconization method according to claim 1, characterized in that the aging process is performed after the nickel hydroxide cobalt cake is crushed to a particle size of 10 to 20 mm.
3. Desilication method according to claim 2, characterized in that it comprises the following steps:
crushing the nickel cobalt hydroxide cake until the granularity is 10-15 mm, and adjusting the water content to be 60-65%;
mixing the crushed nickel cobalt hydroxide cake with 45-55% sulfuric acid, wherein 0.8-1.5 ml of sulfuric acid is correspondingly added into each gram of nickel cobalt hydroxide biscuit ore, then, curing is carried out for 1-2.5 h at the temperature of 80-90 ℃ to obtain cured slurry, and then, water is supplemented to a constant volume until the pH value is 1.5-2;
adding the reducing agent into the cured slurry to carry out the reduction reaction to obtain the reduction slurry;
and carrying out solid-liquid separation on the reduction slurry to obtain the desiliconization leaching solution and the silicon-containing slag.
4. The desilication method according to any one of claims 1 to 3, characterized in that the time of the reduction reaction is 0.5 to 1 hour.
5. The method according to any one of claims 1 to 3, wherein the solid-liquid separation process is performed by means of filter press filtration.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201910797647.4A CN110423898B (en) | 2019-08-27 | 2019-08-27 | Desiliconization method in laterite nickel ore leaching process |
| PH12020050259A PH12020050259A1 (en) | 2019-08-27 | 2020-08-07 | Desilication method in laterite nickel ore leaching process |
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| CN201910797647.4A CN110423898B (en) | 2019-08-27 | 2019-08-27 | Desiliconization method in laterite nickel ore leaching process |
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| CN110423898B true CN110423898B (en) | 2022-03-01 |
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| CN111519019B (en) * | 2020-06-04 | 2022-02-08 | 中国恩菲工程技术有限公司 | Method for desiliconizing hydrated oxide valuable element during leaching |
| CN115232967A (en) * | 2022-06-01 | 2022-10-25 | 金川集团镍盐有限公司 | Method for re-leaching nickel hydroxide waste residue with sulfuric acid |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102212690A (en) * | 2011-06-08 | 2011-10-12 | 广西银亿科技矿冶有限公司 | Method for purifying lateritic nickel ore leach liquor |
| CN103757260A (en) * | 2014-01-13 | 2014-04-30 | 中国恩菲工程技术有限公司 | Treatment method of nickel-containing eluvial ores |
| CN106191442A (en) * | 2016-08-23 | 2016-12-07 | 金川集团股份有限公司 | A kind of method of nickel solution deeply purifying and removing silicon |
| CN106745342A (en) * | 2016-11-29 | 2017-05-31 | 吉林吉恩镍业股份有限公司 | The preparation method for producing nickel chloride is leached by raw material sulphuric acid of rough nickel hydroxide |
| CN106834675A (en) * | 2017-01-24 | 2017-06-13 | 烟台金钪稀贵金属材料有限公司 | A kind of combined leaching process of cobalt hydroxide nickel and cobalt sulfide nickel |
| CN106834722A (en) * | 2017-01-24 | 2017-06-13 | 烟台金钪稀贵金属材料有限公司 | With extraction iron oxide, aluminum oxide, the method for scandium oxide in a kind of utilization cobalt hydroxide nickel fibers slag and titanium white waste acid |
-
2019
- 2019-08-27 CN CN201910797647.4A patent/CN110423898B/en active Active
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2020
- 2020-08-07 PH PH12020050259A patent/PH12020050259A1/en unknown
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102212690A (en) * | 2011-06-08 | 2011-10-12 | 广西银亿科技矿冶有限公司 | Method for purifying lateritic nickel ore leach liquor |
| CN103757260A (en) * | 2014-01-13 | 2014-04-30 | 中国恩菲工程技术有限公司 | Treatment method of nickel-containing eluvial ores |
| CN106191442A (en) * | 2016-08-23 | 2016-12-07 | 金川集团股份有限公司 | A kind of method of nickel solution deeply purifying and removing silicon |
| CN106745342A (en) * | 2016-11-29 | 2017-05-31 | 吉林吉恩镍业股份有限公司 | The preparation method for producing nickel chloride is leached by raw material sulphuric acid of rough nickel hydroxide |
| CN106834675A (en) * | 2017-01-24 | 2017-06-13 | 烟台金钪稀贵金属材料有限公司 | A kind of combined leaching process of cobalt hydroxide nickel and cobalt sulfide nickel |
| CN106834722A (en) * | 2017-01-24 | 2017-06-13 | 烟台金钪稀贵金属材料有限公司 | With extraction iron oxide, aluminum oxide, the method for scandium oxide in a kind of utilization cobalt hydroxide nickel fibers slag and titanium white waste acid |
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| PH12020050259A1 (en) | 2021-03-15 |
| CN110423898A (en) | 2019-11-08 |
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