CN101759233B - Method for recovering cobalt from cobalt sulfate solution - Google Patents
Method for recovering cobalt from cobalt sulfate solution Download PDFInfo
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- CN101759233B CN101759233B CN2008102388444A CN200810238844A CN101759233B CN 101759233 B CN101759233 B CN 101759233B CN 2008102388444 A CN2008102388444 A CN 2008102388444A CN 200810238844 A CN200810238844 A CN 200810238844A CN 101759233 B CN101759233 B CN 101759233B
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Abstract
The invention provides a method for recovering cobalt from a cobalt sulfate solution, comprising the following steps of: (A) mixing calcium oxide and/or calcium hydroxide with calcium sulfate used as a seed crystal; (B) mixing the mixture of the calcium oxide and/or the calcium hydroxide and the calcium sulfate with the cobalt sulfate solution to generate a calcium sulfate sediment and a cobalt hydroxide sediment; and (C) separating the calcium sulfate and the cobalt hydroxide. The method for recovering the cobalt hydroxide from the cobalt sulfate solution can recover the cobalt from the cobalt sulfate solution in the mode of low cost and pollution to recycle resources and also can produce the calcium sulfate (plaster), thereby reducing the production cost and relieving the environmental pollution.
Description
Technical field
The present invention relates to reclaim the method for cobalt, concrete, relate to the method that from cobalt sulfate solution, reclaims cobalt.
Background technology
At present, in many industrial circles, often produce the waste liquid that contains cobalt in a large number.For example, in hydrometallurgy process to cobalt-containing ore or contain the cobalt material and carry out the sulfuric acid leaching and can produce the solution that contains rose vitriol.Traditional treatment process is to use chemical agent such as sodium hydroxide, yellow soda ash or vulcanizing agent precipitate cobalt oxyhydroxide or sulfide from the solution that contains cobalt, but the price of reagent is higher or toxic.
Traditional method uses hydrogen sulfide and other vulcanizing agents to precipitate cobaltous sulfide from the solution that contains cobalt.Though this technology can obtain high-quality product, operation is carried out in the toxicity environment, has unsafe factor, the production cost height.Use other vulcanizing agents for example sodium sulphite then product purity is low, the production cost height, production environment is bad.
Summary of the invention
Purpose of the present invention is intended to one of solve the aforementioned problems in the prior at least.
For this reason, one object of the present invention be to propose a kind of can the low-cost method that from cobalt sulfate solution, reclaims cobalt.
The method that reclaims cobalt from cobalt sulfate solution according to the embodiment of the invention may further comprise the steps:
A) calcium oxide and/or calcium hydroxide are mixed with calcium sulfate as crystal seed,
B) mixture with calcium oxide and/or calcium hydroxide and calcium sulfate mixes with cobalt sulfate solution, to generate calcium sulfate precipitation and cobaltous hydroxide precipitation; And
C) separating calcium sulphate and cobaltous hydroxide.
The method that from cobalt sulfate solution, reclaims cobalt according to the embodiment of the invention, owing in the reaction system of rose vitriol and calcium oxide and/or calcium hydroxide, there is calcium sulfate as crystal seed, the granularity of the calcium sulfate that generates in can the augmenting response process, thereby can utilize the granularity of calcium sulfate precipitation and the difference of cobaltous hydroxide granularity, follow-up separating calcium sulphate at an easy rate and cobaltous hydroxide precipitation, and can improve the sedimentary rate of recovery of cobaltous hydroxide and purity.Therefore, the present invention can reclaim cobalt with low-cost, oligosaprobic mode from cobalt sulfate solution, reach the recycling of resource, and attached product calcium sulfate (gypsum), and reducing production costs alleviates environmental pollution.
In one embodiment of the invention, the mixture of calcium oxide and/or calcium hydroxide and calcium sulfate is mixed with cobalt sulfate solution comprise cobalt sulfate solution is joined in calcium oxide and/or calcium hydroxide and the mixture as the calcium sulfate of crystal seed.The present inventor finds, by cobalt sulfate solution being joined in calcium oxide and/or calcium hydroxide and the mixture as the calcium sulfate of crystal seed, for example splash into wherein, can further improve the granularity of the calcium sulfate precipitation of reaction efficiency and generation, thus more separate easily calcium sulfate and cobaltous hydroxide.
Described cobalt sulfate solution is the leach liquor that contains cobalt and the leaching of metal concentrate sulfuric acid.Owing in containing the leaching of cobalt concentrate sulfuric acid, can produce the solution of a large amount of sulfur acid cobalts, the effect of therefore low-cost recovery cobalt technology in the industrial application that concentrate sulfuric acid leaches is better.In the further embodiment of the present invention, described cobalt sulfate solution is the solution of leach liquor through obtaining after purifying, and has so not only obtained the metal ingredient in the ore effectively, and can reclaim the cobalt in the waste liquid that leaches as sulfuric acid.Purification comprises at least a metal of removing in the leach liquor, and for example iron, copper, nickel, chromium thus, not only can reclaim compositions such as iron, copper, nickel, chromium, and reclaim the cobalt in the ore, have both reduced pollution, again recycle resource.
In one embodiment of the invention, calcium sulfate as crystal seed prepares by alkali-metal vitriol and calcium oxide and/or calcium hydroxide reaction, the resulting like this calcium sulfate as crystal seed can make easier being attached on it of calcium sulfate in the cobalt sulfate solution, generate the precipitation of larger particle, thereby separate easilier with the precipitation cobaltous hydroxide.In further embodiment, described alkali-metal vitriol is sodium sulfate, can save cost like this.
In one embodiment of the invention, as the calcium sulfate of crystal seed by cobalt sulfate solution and calcium oxide and/or calcium hydroxide reaction obtain calcium sulfate and cobaltous hydroxide, separating calcium sulphate and cobaltous hydroxide, and isolating calcium sulfate washed after obtain.Can save alkali-metal vitriol like this, save cost.
In one embodiment of the invention, further comprise isolated cobaltous hydroxide is washed and/or drying, can improve the purity of institute's separation of hydrogen cobalt oxide like this, and be convenient to prolonged preservation.
In one embodiment of the invention, further comprise with separating the cobaltous hydroxide that obtains and produce the cobalt goods, can utilize further cobaltous hydroxide like this, improve the economic value added that reclaims cobaltous hydroxide.
Additional aspect of the present invention and advantage part in the following description provide, and part will become obviously from the following description, or recognize by practice of the present invention.
Description of drawings
Fig. 1 is the schema of the method for cobalt that reclaims from cobalt sulfate solution of first embodiment of the invention;
Fig. 2 is the schema of the method for cobalt that reclaims from cobalt sulfate solution of second embodiment of the invention;
Fig. 3 is the schema of the method for cobalt that reclaims from cobalt sulfate solution of third embodiment of the invention;
Fig. 4 is the schema of the method for cobalt that reclaims from cobalt sulfate solution of fourth embodiment of the invention;
Fig. 5 is the schema of the method for cobalt that reclaims from cobalt sulfate solution of fifth embodiment of the invention.
Embodiment
Describe embodiments of the invention below in detail, the example of described embodiment is shown in the drawings, is exemplary below by the embodiment that is described with reference to the drawings, and only is used to explain the present invention, and can not be interpreted as limitation of the present invention.
Need to prove that term " calcium oxide and/or calcium hydroxide " is meant and can uses calcium oxide (unslaked lime) also can use calcium hydroxide (white lime) in the present invention, also can add the mixture of the two.In actually operating, can water assimilation of quicklime using (CaO), thus obtaining milk of lime, principal reaction is CaO+H
2O=Ca (OH)
2, the mixture of milk of lime as calcium oxide and calcium hydroxide used.
Fig. 1 shows the schema according to the method for cobalt that reclaims of first embodiment of the invention from cobalt sulfate solution.According to shown in Figure 1, at first calcium oxide and/or calcium hydroxide are mixed with calcium sulfate as crystal seed.Then add cobalt sulfate solution in resulting mixture, to generate calcium sulfate precipitation and cobaltous hydroxide precipitation, its reaction that mainly takes place is:
CoSO
4+Ca(OH)
2＝CaSO
4+Co(OH)
2，
Last separating calcium sulphate and cobaltous hydroxide.
As mentioned above, rose vitriol in the cobalt sulfate solution and calcium hydroxide reaction generate calcium sulfate precipitation and cobaltous hydroxide precipitation.Yet the sedimentary particle of calcium sulfate precipitation and cobaltous hydroxide is all very little, and the granularity difference is smaller, and more specifically, calcium sulfate precipitation is a crystalline form, and cobaltous hydroxide is a gel, and cobaltous hydroxide is coated on the calcium sulfate, so the two is difficult to separate.In addition, when rose vitriol and calcium hydroxide reacted, the sedimentary formation of cobaltous hydroxide had limited the further increase of calcium sulfate granularity, thereby has further increased separating difficulty.
According to embodiments of the invention, in the reaction system that rose vitriol and calcium hydroxide react, contain calcium sulfate as crystal seed, therefore, when rose vitriol and calcium hydroxide react, formed calcium sulfate precipitation can be formed on the crystal seed, thereby the granularity of calcium sulfate precipitation can further increase, and promptly forms the calcium sulfate precipitation of volume particle size, separating between being convenient to follow-up calcium sulfate thus and cobaltous hydroxide precipitating.
The source of the employed in the present invention calcium sulfate as crystal seed is not restricted, both can be the ready-made calcium sulfate of buying from the market, also can be the calcium sulfate that obtains by independent chemical reaction, the product calcium sulfate that also can be in this technology to be generated.
In addition, in actually operating, at first cobalt sulfate solution is joined calcium oxide and/or calcium hydroxide and mixing as the calcium sulfate slurry of crystal seed, then the cobalt sulfate solution adding is for example splashed in the described mixture, can further improve the granularity of the calcium sulfate precipitation of reaction efficiency and generation like this.
With reference to figure 2, in one embodiment of the invention, be to use calcium sulfate precipitation that alkali-metal vitriol and calcium oxide and/or calcium hydroxide reaction generated in that to separate the back resulting as the calcium sulfate of crystal seed.The contriver finds that the calcium sulfate that uses this method to obtain can obviously increase the granularity of the calcium sulfate precipitation of generation as crystal seed.In addition, in a further embodiment, employed alkali-metal vitriol is sodium sulfate, because the cost of sodium sulfate is low, the sodium hydroxide that is generated is solvable and can reuse, and therefore when can being convenient to separation of hydrogen sodium oxide and calcium sulfate, has also reduced cost.
With reference to figure 4, in one embodiment of the invention, as the calcium sulfate of crystal seed is to obtain calcium sulfate with cobaltous hydroxide, separating calcium sulphate and cobaltous hydroxide, then the calcium sulfate after separating is carried out obtaining after the classification washing by cobalt sulfate solution and calcium oxide and/or calcium hydroxide reaction, do not need extra independent preparation calcium sulfate crystal seed like this and saved alkali-metal vitriol, therefore further save to produce and produce this.For example, can in the part of sulfuric acid cobalt liquor, add a certain amount of calcium oxide and/or calcium hydroxide earlier, obtain calcium sulfate and cobaltous hydroxide precipitation, from this reaction system, isolate calcium sulfate and cobaltous hydroxide then, and the calcium sulfate precipitation that obtains is washed the calcium sulfate that obtains as crystal seed.
In addition, as mentioned above, at the beginning of technological process, also can be earlier in cobalt sulfate solution, add the calcium sulfate buied from market as crystal seed, then by reaction, separate the calcium sulfate that obtains and just can be used as after the crystal seed of use.
In an embodiment of the present invention, calcium oxide and/or calcium hydroxide are mixed with calcium sulfate as crystal seed, both can use calcium oxide (unslaked lime), also can use calcium hydroxide (white lime), also can use the mixture of the two.Concrete, can water assimilation of quicklime using (CaO), thus obtaining milk of lime, principal reaction is CaO+H
2O=Ca (OH)
2More specifically, unslaked lime adds less water to be made its heating, aquation, is paste, and after thermopositive reaction finished substantially, thin up was sized mixing, and can prolong digestion time under the situation of time permission.When using commercial lime, except that prolonging digestion time, also need to sieve, to remove unreacted residue.It will be appreciated by those skilled in the art that, calcium oxide and/or calcium hydroxide are mixed with calcium sulfate as crystal seed, both milk of lime can have been joined in the calcium sulfate cobalt sulfate solution as crystal seed, also the calcium sulfate cobalt sulfate solution as crystal seed can have been joined in the milk of lime.In one embodiment of the invention, be that milk of lime is joined in the calcium sulfate cobalt sulfate solution as crystal seed, the contriver finds to adopt this method can improve efficient at follow-up rose vitriol and calcium hydroxide reaction, further facilitates later separation cobaltous hydroxide and calcium sulfate.
Milk of lime is mixed with cobalt sulfate solution, and stir, thereby rose vitriol and milk of lime react, and have generated throw out calcium sulfate and cobaltous hydroxide, principal reaction is CoSO
4+ Ca (OH)
2=Co (OH)
2↓+CaSO
4↓.
Calcium sulfate can be with CaSO
4XH
2The crystallized form of O (x is about 2/3) is precipitated out, because the granularity of the size ratio cobaltous hydroxide of calcium sulfate wants big, and owing to added the calcium sulfate crystal seed, compares with not adding crystal seed, the granulometric facies of calcium sulfate can further increase for the granularity of cobaltous hydroxide.Therefore can easily calcium sulfate be separated with cobaltous hydroxide according to two kinds of sedimentary granular size differences.
In addition, in one embodiment of the invention, in order to obtain the higher cobaltous hydroxide of purity, and prolonged preservation, isolated cobaltous hydroxide is washed and/or dry.Washings can adopt deionized water, can prevent that like this cobaltous hydroxide suspension from flocculating.
With reference to figure 5, in one embodiment of the invention, separate the cobaltous hydroxide that obtains and to be used to prepare the cobalt goods.
With reference to figure 4, in one embodiment of the invention, as previously mentioned, the calcium sulfate that separation is obtained can be used as crystal seed and turns back in the reaction system after removing the impurity (as cobaltous hydroxide) on surface through washing.In addition, resulting calcium sulfate can also be used to prepare sulfuric acid and cement.
The source of cobalt sulfate solution is not subjected to any restriction in the present invention, as long as contain rose vitriol in its solution.With reference to figure 3, in one embodiment of the invention, cobalt sulfate solution is to contain the concentrate of cobalt or contain the leach liquor that cobalt material sulfuric acid leaches.Using at present sulfuric acid that ore is carried out that acidleach goes out is that development is very fast at present, uses very wide wet process smelting technique, and still the sulfate waste liquid that is produced also becomes the factor that environment is made a very bad impression.Traditionally, the solution that contains rose vitriol not only is untreated as waste liquid, and cobalt wherein abandons as waste liquid.Consider that mining industry can produce the waste liquid of several tons even tens of tons every day, therefore use treatment process of the present invention can obtain extraordinary economic benefit, greatly reduce production cost.
In the further embodiment of the present invention, the cobalt sulfate solution of use is a sulphuric leachate through the solution that obtains after purifying, and promptly reclaims other compositions in (removals) leach liquor earlier, reclaims the interior cobalt that exists with the rose vitriol form of waste liquid again.For example, " purification " can be at least a metal of removing in the sulphuric leachate, for example iron, copper, nickel and chromium, but the present invention is not limited to remove mentioned component.Because the purification in the sulfuric acid leaching process is known for those of ordinary skill in the art, gives unnecessary details no longer in detail here.
Although illustrated and described embodiments of the invention, for the ordinary skill in the art, be appreciated that without departing from the principles and spirit of the present invention and can carry out multiple variation, modification, replacement and modification that scope of the present invention is by claims and be equal to and limit to these embodiment.
Claims (10)
1. method that reclaims cobalt from cobalt sulfate solution may further comprise the steps:
A) calcium oxide and/or calcium hydroxide are mixed with calcium sulfate as crystal seed;
B) mixture with calcium oxide and/or calcium hydroxide and calcium sulfate mixes with cobalt sulfate solution, to generate calcium sulfate precipitation and cobaltous hydroxide precipitation; And
C) separating calcium sulphate and cobaltous hydroxide.
2. the method that from cobalt sulfate solution, reclaims cobalt according to claim 1, it is characterized in that, the mixture of calcium oxide and/or calcium hydroxide and calcium sulfate is mixed with cobalt sulfate solution comprise cobalt sulfate solution is joined in calcium oxide and/or calcium hydroxide and the mixture as the calcium sulfate of crystal seed.
3. the method that reclaims cobalt from cobalt sulfate solution according to claim 1 is characterized in that, described cobalt sulfate solution is to contain cobalt concentrate or contain the leach liquor that cobalt material sulfuric acid leaches.
4. the method that reclaims cobalt from cobalt sulfate solution according to claim 3 is characterized in that, described cobalt sulfate solution is the solution of described leach liquor through obtaining after purifying.
5. the method that reclaims cobalt from cobalt sulfate solution according to claim 4 is characterized in that described purification comprises at least a metal of removing in the leach liquor.
6. the method that reclaims cobalt from cobalt sulfate solution according to claim 1 is characterized in that, prepares by alkali-metal vitriol and calcium oxide and/or calcium hydroxide reaction as the calcium sulfate of crystal seed.
7. the method that reclaims cobalt from cobalt sulfate solution according to claim 6 is characterized in that described alkali-metal vitriol is sodium sulfate.
8. the method that from cobalt sulfate solution, reclaims cobalt according to claim 1, it is characterized in that, as the calcium sulfate of crystal seed obtain calcium sulfate and cobaltous hydroxide, separating calcium sulphate and cobaltous hydroxide by cobalt sulfate solution and calcium oxide and/or calcium hydroxide reaction and isolating calcium sulfate washed after obtain.
9. the method that reclaims cobalt from cobalt sulfate solution according to claim 1 is characterized in that, further comprises isolated cobaltous hydroxide is washed and drying.
10. the method that reclaims cobalt from cobalt sulfate solution according to claim 1 is characterized in that, further comprises with separating the cobaltous hydroxide that obtains producing the cobalt goods.
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| CN2008102388444A CN101759233B (en) | 2008-12-02 | 2008-12-02 | Method for recovering cobalt from cobalt sulfate solution |
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| CN2008102388444A CN101759233B (en) | 2008-12-02 | 2008-12-02 | Method for recovering cobalt from cobalt sulfate solution |
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| CN101759233B true CN101759233B (en) | 2011-08-10 |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103011229A (en) * | 2012-12-13 | 2013-04-03 | 国家海洋局天津海水淡化与综合利用研究所 | Method for preparing transition element hydroxide by using calcium hydroxide |
| CN108298600A (en) * | 2018-04-13 | 2018-07-20 | 厦门大学 | A kind of environment-friendly preparation method thereof of two dimension hydroxide nano piece |
| CN109292831A (en) * | 2018-11-23 | 2019-02-01 | 湖南中伟新能源科技有限公司 | A kind of processing method of cobaltosic oxide production waste water |
| CN110669931B (en) * | 2019-09-25 | 2021-04-27 | 宁波弗镁瑞环保科技有限公司 | Method for removing cobalt by oxidizing nickel sulfate solution |
| CN112186170B (en) * | 2020-08-26 | 2022-04-22 | 南通金通储能动力新材料有限公司 | Method for reducing calcium content in nickel-cobalt-manganese ternary precursor |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1533741A (en) * | 1924-06-13 | 1925-04-14 | Bethlehem Steel Corp | Metallurgical process |
| CN1184858A (en) * | 1996-12-13 | 1998-06-17 | 抚顺石油化工公司洗涤剂化工厂 | Method for recovering cobalt from cobalt contg. waste catalyst used is carbonylation syntehsizing process |
| US5855858A (en) * | 1993-07-29 | 1999-01-05 | Cominco Engineering Services Ltd. | Process for the recovery of nickel and/or cobalt from an ore or concentrate |
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2008
- 2008-12-02 CN CN2008102388444A patent/CN101759233B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1533741A (en) * | 1924-06-13 | 1925-04-14 | Bethlehem Steel Corp | Metallurgical process |
| US5855858A (en) * | 1993-07-29 | 1999-01-05 | Cominco Engineering Services Ltd. | Process for the recovery of nickel and/or cobalt from an ore or concentrate |
| CN1184858A (en) * | 1996-12-13 | 1998-06-17 | 抚顺石油化工公司洗涤剂化工厂 | Method for recovering cobalt from cobalt contg. waste catalyst used is carbonylation syntehsizing process |
Non-Patent Citations (2)
| Title |
|---|
| 刘平.石膏晶种添加法在精盐生产中应用浅析.《柴达木开发研究》.1991,(第4期),61-63. * |
| 江丽等.从二次电池废泡沫式镍极板中回收钴.《湿法冶金》.2001,第20卷(第2期),92-95. * |
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