CN102230086A - Process for simultaneously leaching cobalt and nickel from vulcanized slag - Google Patents
Process for simultaneously leaching cobalt and nickel from vulcanized slag Download PDFInfo
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- CN102230086A CN102230086A CN2011101699359A CN201110169935A CN102230086A CN 102230086 A CN102230086 A CN 102230086A CN 2011101699359 A CN2011101699359 A CN 2011101699359A CN 201110169935 A CN201110169935 A CN 201110169935A CN 102230086 A CN102230086 A CN 102230086A
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Abstract
本发明提供了一种从锰矿浸出工艺除重金属硫化渣中同时浸出钴、镍的新方法，属于钴、镍回收技术领域。本发明的基本步骤是：在反应器中加入硫化渣，然后加入硝酸和硫酸的混酸溶液，用水调制矿浆液固比为2∶1～7∶1；在45～100℃温度下搅拌反应20～120分钟得到反应浸出液，钴、镍的浸出率超过90％。本发明的优点是完全湿法浸出，避免了焙烧所带来的高能耗和高污染，浸出工艺条件温和，反应速度快，废渣量少，过滤容易。The invention provides a new method for simultaneously leaching cobalt and nickel from a manganese ore leaching process for removing heavy metal sulfide slag, belonging to the technical field of cobalt and nickel recovery. The basic steps of the present invention are: add sulfide slag into the reactor, then add the mixed acid solution of nitric acid and sulfuric acid, adjust the liquid-solid ratio of ore pulp with water to be 2:1～7:1; stir and react at 45～100℃ for 20～ The reaction leaching solution is obtained in 120 minutes, and the leaching rate of cobalt and nickel exceeds 90%. The invention has the advantages of complete wet leaching, avoiding high energy consumption and high pollution caused by roasting, mild leaching process conditions, fast reaction speed, less waste residue, and easy filtration.
Description
Technical field:
The present invention relates to a kind of technology that from manganese ore extract technology removing heavy metals sulfuration slag, leaches cobalt, nickel, particularly in sulfuric acid medium, leach the method for cobalt and nickel in the sulfuration slag simultaneously with nitric acid as oxidant.
Background technology:
China's manganese resource that is richly stored with in manganese ore, contains nickel, the cobalt of ultramicron.General manganese ore is after pulverizing, gravity treatment, magnetic separation, and manganese content is about 20.0%, and nickel content is about 0.01%～0.10%, and cobalt contents is about 0.01%～0.08%.Manganese ore leaches through sulfuric acid, generates the vitriol of various metals.Leach liquor in order to remove the heavy metal that contains in the filtrate, adds Methyl disulfide for amido sodium formiate (SDD) solution to filtrate after neutralization, press filtration, make heavy metal ion and SDD generation combination reaction generation throw outs such as nickel cobalt, and this throw out is called as the sulfuration slag.General nickeliferous 0.5%～3.0% in the slag, contain cobalt 0.3%～2.0%, contain manganese 5.0%～7.0%, iron content 4.0%～7.0%, siliceous about 20.0%.In sulfidation, the formation reaction formula of nickel cobalt sulfide is: Ni
2++ 2Nay=Ni (y)
2+ 2Na
+, Co
2++ 2Nay=Co (y)
2+ 2Na
+(in the formula, y is the anion radical of SDD).
In the manganese ore extract technology, the method that cobalt, nickel reclaim in the sulfuration slag of employing SDD precipitation of heavy metals is few, and wet method leaches and yet there are no report completely.At present, from the sulfuration slag of SDD precipitation of heavy metals, reclaim cobalt and nickel, generally adopt flotation, roasting, extract technology.Reported some relevant documents as open source literature, taken passages as follows by retrieval:
1. [application (patent) number] CN200710049289.6[title] from manganese ore, reclaim method [application (patent right) people] a kind of method that from manganese ore, reclaims micro-nickel, cobalt in Xia Lei town, Daxin County, Guangxi Daxin Zhuxin Manganese Industry Co., Ltd. [address] 532315 Guangxi Zhuang Autonomous Region [summary] of micro-nickel, cobalt, with the liquid after the sulphuric leachate deironing of manganic concerntrate again behind the removing heavy metals sulfuration slag of gained be raw material, the sulfuration slag is added water, and to be made into weight concentration be 20～30% ore pulp, the restir or the stirring 20～80 minutes of heating, collect scum silica frost, the filtration of bleeding.Filter residue 40～80 minutes time, promptly gets the concentrate that is rich in nickel, cobalt 600～800 ℃ of following roastings.Use method of the present invention from manganese ore, to reclaim micro-nickel and cobalt; gained concentrate product nickel content can reach more than 13.94%; cobalt contents can reach more than 10.72%; nickel, cobalt metal recovery rate are near 100%; and in removal process, need not add any chemical agent or additive; can not produce pollution, that has accomplished resource makes full use of and has protected environment.
2. [autograph] is good for the coloured mining and metallurgy .2006 of resource and environment institute of not big [mechanism] Guangxi University [periodical name] less from Study of flotation [author] the DKNY Na horse that certain manganese ore soaks recovery cobalt the slag, 22 supplementary issues: 8-9[digest] reclaim cobalt the slag for soaking from manganese ore, research add butyl xanthate, amyl group xanthate, Y89 xanthate, four kinds of collecting agents of butyl ammonium aerofloat and use water glass, sodium sulphite, Sodium hexametaphosphate 99, sodium humate, starch, dextrin, tannic acid as inhibitor to soaking the manganese slag and roughly select and open a way selected influence.The result shows, is not adding under the collecting agent direct flotation condition, and the cobalt rate of recovery of soaking in the manganese slag reaches more than 94%, and concentrate grade reaches 0.89%, and concentration ratio reaches 3.07.An amount of xanthate and the black powder class collecting agent of adding changes under the little situation in the rate of recovery, can both suitably improve concentrate grade.Seven kinds of inhibitor such as water glass have stronger inhibition ability to soaking the manganese slag flotation, can both suitably improve concentrate grade.Open a way and selectedly can keep significantly improving Floatation Concentrate Grade under the higher recovery condition.
Recognize from above-mentioned result for retrieval, the open source literature introduction mainly be: with method enriched in cobalt, the nickel of mineral floating, roasting becomes the oxide compound concentrate to carry out acidleach again, removal of impurities, whole flow process complexity, float product contains a large amount of sulphur, nitrogen compound, and roasting process not only can produce the obnoxious flavour contaminate environment, and power consumption is bigger.In sum, reclaim cobalt and nickel in the removing heavy metals sulfuration slag in the manganese ore extract technology at present, mainly still adopt flotation, pyrogenic process, hydrometallurgy bonded form, the energy consumption height produces large quantity of exhaust gas and sewage in the production process.
Summary of the invention:
The purpose of this invention is to provide that a kind of raw material sources are easy, cheap, manufacturing requirements is lower, from the sulfuration slag, leach the method for cobalt and nickel simultaneously.It is characterized in that utilizing nitric acid as oxidant, in sulfuric acid medium, extract cobalt and nickel in the manganese ore extract technology removing heavy metals sulfuration slag, prepare the method for rose vitriol, nickel sulfate solution.
Above-mentioned said sulfuration slag is meant with the throw out of Methyl disulfide for the heavy metal in amido sodium formiate (SDD) the precipitation manganese ore leach liquor, and is general nickeliferous 0.5%～3.0% in the slag, contains cobalt 0.3%～2.0%.
The present invention realizes like this, in reactor, add the sulfuration slag, 0.42～1.4 times of concentration of adding sulfuration slag amount is 68% nitric acid, and 0.18～1.8 times of concentration of adding sulfuration slag amount is 98% sulfuric acid then, and water modulation ore pulp to liquid-solid ratio is 2: 1～7: 1; Stirring reaction obtained reacting leach liquor in 20～120 minutes under 45～100 ℃ of temperature; Remove impurity such as calcium in the solution, magnesium, iron, manganese by the method for known chemical subtraction then, obtain purified rose vitriol, nickel sulfate solution, the leaching yield of cobalt, nickel surpasses 90%, solution can further be used known method separation of cobalt, nickel, also can be directly used in the precursor of preparation cobalt nickel material.
Cobalt in the present invention and the existing manganese ore extract technology in the removing heavy metals sulfuration slag, the recovery technology of nickel are compared, and its outstanding substantive distinguishing features and obvious improvement is:
(1) hydrometallurgical processes has completely been avoided high energy consumption that roasting brought and high pollution, has environmental protection and economic double benefit.
(2) compare with high temperature leaching oxide compound concentrate, the reaction conditions gentleness, speed of response is fast, and leaching process waste residue amount is few, filters easily.
Embodiment:
Embodiment 1
Add sulfuration slag (forming as shown in table 1) in reactor, 0.56 times of concentration of adding sulfuration slag amount is 68% nitric acid, and 0.74 times of concentration of adding sulfuration slag amount is 98% sulfuric acid then, and water modulation ore pulp to liquid-solid ratio is 5: 1; Stirring reaction obtained reacting leach liquor in 40 minutes under 90 ℃ of temperature, and the Co leaching yield of sulfuration slag reaches 98%, and the leaching yield of Ni reaches 96%.
The analysis of table 1 sulfuration slag ingredient
| Composition | Co | Ni | Mn | Fe | Cu | Mg | Ca | Cr | S |
| Content (%) | 0.75 | 1.10 | 6.15 | 4.88 | 0.041 | 1.50 | 7.56 | 0.035 | 16.01 |
Embodiment 2
Add sulfuration slag (forming as shown in table 1) in reactor, 1.4 times of concentration of adding sulfuration slag amount are 68% nitric acid, and 0.18 times of concentration of adding sulfuration slag amount is 98% sulfuric acid then, and water modulation ore pulp to liquid-solid ratio is 2: 1; Stirring reaction obtained reacting leach liquor in 30 minutes under 70 ℃ of temperature, and the Co leaching yield of sulfuration slag reaches 93%, and the leaching yield of Ni reaches 91%.
Embodiment 3
Add sulfuration slag (forming as shown in table 1) in reactor, 0.42 times of concentration of adding sulfuration slag amount is 68% nitric acid, and 1.8 times of concentration of adding sulfuration slag amount are 98% sulfuric acid then, and water modulation ore pulp to liquid-solid ratio is 7: 1; Stirring reaction obtained reacting leach liquor in 120 minutes under 45 ℃ of temperature, and the Co leaching yield of sulfuration slag reaches 95%, and the leaching yield of Ni reaches 93%.
Embodiment 4
Add sulfuration slag (forming as shown in table 1) in reactor, 0.7 times of concentration of adding sulfuration slag amount is 68% nitric acid, and 0.9 times of concentration of adding sulfuration slag amount is 98% sulfuric acid then, and water modulation ore pulp to liquid-solid ratio is 4: 1; Stirring reaction obtained reacting leach liquor in 20 minutes under 50 ℃ of temperature, and the Co leaching yield of sulfuration slag reaches 90%, and the leaching yield of Ni reaches 93%.
Embodiment 5
Add sulfuration slag (forming as shown in table 1) in reactor, 0.56 times of concentration of adding sulfuration slag amount is 68% nitric acid, and 1.08 times of concentration of adding sulfuration slag amount are 98% sulfuric acid then, and water modulation ore pulp to liquid-solid ratio is 3: 1; Stirring reaction obtained reacting leach liquor in 60 minutes under 100 ℃ of temperature, and the Co leaching yield of sulfuration slag reaches 96%, and the leaching yield of Ni reaches 94%.
Claims (3)
1. method that from manganese ore extract technology removing heavy metals sulfuration slag, leaches cobalt, nickel simultaneously, it is characterized in that with sulfuration slag amount 0.42～1.4 times of concentration being 68% nitric acid, with sulfuration slag amount 0.18～1.8 times of concentration 98% sulfuric acid, water modulation ore pulp to liquid-solid ratio is 2: 1～7: 1, leaching sulfuration slag under 45～100 ℃ of temperature, stirring reaction obtained rose vitriol, nickel sulfate solution in 20～120 minutes.
2. method according to claim 1, it is characterized in that vulcanizing slag is that manganese ore leaches through sulfuric acid, leach liquor adds Methyl disulfide for amido sodium formiate (SDD) solution through neutralization, after the press filtration to filtrate, makes heavy metal ion such as nickel cobalt and SDD that the throw out of combination reaction generation take place.General nickeliferous 0.5%～3.0% in the slag, contain cobalt 0.3%～2.0%.
3. method according to claim 1, the Step By Condition of its preparation rose vitriol, nickel sulfate solution is as follows:
Add the sulfuration slag in reactor, add 0.42～1.4 times of concentration of sulfuration slag amount and be 68% nitric acid and 0.18～1.8 times of concentration of sulfuration slag amount and be 98% sulfuric acid, water modulation ore pulp liquid-solid ratio is 2: 1～7: 1; Stirring reaction obtained reacting leach liquor in 20～120 minutes under 45～100 ℃ of temperature.
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| CN2011101699359A CN102230086A (en) | 2011-06-23 | 2011-06-23 | Process for simultaneously leaching cobalt and nickel from vulcanized slag |
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|---|---|---|---|
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014008540A1 (en) * | 2012-07-09 | 2014-01-16 | Direct Nickel Pty Ltd | Method for the recovery of nickel from sulphide ores |
| CN107012337A (en) * | 2017-04-01 | 2017-08-04 | 贵州大龙汇成新材料有限公司 | The method of enriching and recovering nickel cobalt from manganese-containing waste |
| CN107723469A (en) * | 2017-08-31 | 2018-02-23 | 广东佳纳能源科技有限公司 | A kind of cobalt smelting process vulcanized slag recycling processing method |
| WO2025107108A1 (en) * | 2023-11-20 | 2025-05-30 | 广东邦普循环科技有限公司 | Method for removing ferrous iron from laterite-nickel ore by high-pressure acid leaching |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101067167A (en) * | 2007-06-08 | 2007-11-07 | 广西大新桂鑫锰业有限公司 | Method for recovering micro-nickel and cobalt from manganese ore |
| CN101298638A (en) * | 2008-06-27 | 2008-11-05 | 中南大学 | Method for collecting nickel and cobalt from laterite-nickel ore lixivium |
-
2011
- 2011-06-23 CN CN2011101699359A patent/CN102230086A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101067167A (en) * | 2007-06-08 | 2007-11-07 | 广西大新桂鑫锰业有限公司 | Method for recovering micro-nickel and cobalt from manganese ore |
| CN101298638A (en) * | 2008-06-27 | 2008-11-05 | 中南大学 | Method for collecting nickel and cobalt from laterite-nickel ore lixivium |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014008540A1 (en) * | 2012-07-09 | 2014-01-16 | Direct Nickel Pty Ltd | Method for the recovery of nickel from sulphide ores |
| CN107012337A (en) * | 2017-04-01 | 2017-08-04 | 贵州大龙汇成新材料有限公司 | The method of enriching and recovering nickel cobalt from manganese-containing waste |
| CN107012337B (en) * | 2017-04-01 | 2019-02-15 | 贵州大龙汇成新材料有限公司 | The method of enriching and recovering nickel cobalt from manganese-containing waste |
| CN107723469A (en) * | 2017-08-31 | 2018-02-23 | 广东佳纳能源科技有限公司 | A kind of cobalt smelting process vulcanized slag recycling processing method |
| WO2025107108A1 (en) * | 2023-11-20 | 2025-05-30 | 广东邦普循环科技有限公司 | Method for removing ferrous iron from laterite-nickel ore by high-pressure acid leaching |
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Application publication date: 20111102 |