CN101760635A - Method for recovering nickel from nickel sulfate solution - Google Patents
Method for recovering nickel from nickel sulfate solution Download PDFInfo
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- CN101760635A CN101760635A CN200810238840A CN200810238840A CN101760635A CN 101760635 A CN101760635 A CN 101760635A CN 200810238840 A CN200810238840 A CN 200810238840A CN 200810238840 A CN200810238840 A CN 200810238840A CN 101760635 A CN101760635 A CN 101760635A
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- nickel
- calcium
- sulfate
- hydroxide
- sulfate solution
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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
- Y02P10/00—Technologies related to metal processing
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Abstract
The invention provides a method for recovering nickel from a nickel sulfate solution, comprising the following steps of: (A) mixing calcium oxide and/or calcium hydrogen carbonate with calcium sulfate used as a seed crystal; (B) mixing the mixture of the calcium oxide and/or the calcium hydrogen carbonate and the calcium sulfate with the nickel sulfate solution to generate a calcium sulfate sediment and a nickel hydrogen carbonate sediment; and (C) separating the calcium sulfate and nickel hydrogen carbonate. The method for recovering the nickel from the nickel sulfate solution can be used for recovering the nickel from the nickel sulfate solution in the mode of low cost and pollution to recycle resources and has the advantages of reducing the production cost and relieving the environmental pollution.
Description
Technical field
The present invention relates to reclaim the method for nickel, concrete, relate to the method that from nickel sulfate solution, reclaims nickel.
Background technology
At present, in many industrial circles, often produce the waste liquid that contains nickel in a large number.For example, in hydrometallurgy process nickel-containing ore or nickel-containing material being carried out acidleach goes out to produce the solution that contains single nickel salt.Traditional treatment process is to use chemical agent such as sodium hydroxide, yellow soda ash or vulcanizing agent coprecipitated nickel hydroxide oxyhydroxide or sulfide from the solution that contains nickel, but the price of reagent is higher or toxic.
A kind of method that reclaims the nickel cobalt from the solution that contains nickel is disclosed among the Chinese patent application CN101094926A, this method comprises: use immiscible organic solvent to handle described solution optionally to absorb most cobalt, the remaining solution that contains nickel, the described solution of nickel that contains that neutralizes is so that described nickel is precipitated as nickel hydroxide.In this patent application, need to use a large amount of organic solvents, easily environment is caused secondary pollution.And at this method kind needs use resin column, so the production cost height, be unsuitable for large-scale industrial application.
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 is to propose a kind of cost effective method that can reclaim nickel from nickel sulfate solution.
The method that reclaims nickel from nickel 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 nickel sulfate solution, to generate calcium sulfate precipitation and nickel hydroxide precipitate; And C) separating calcium sulphate and nickel hydroxide.
The method that from nickel sulfate solution, reclaims nickel according to the embodiment of the invention, owing in the reaction system of single nickel salt 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 nickel hydroxide granularity, separating calcium sulphate and nickel hydroxide precipitate at an easy rate, and can improve the rate of recovery and the purity of nickel hydroxide precipitate.Therefore, the present invention can reclaim nickel with low-cost, oligosaprobic mode from nickel sulfate solution, reach the recycling of resource, 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 nickel sulfate solution comprise nickel 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 nickel 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 nickel hydroxide.
Described nickel sulfate solution is nickeliferous and the leach liquor of metal concentrate sulfuric acid leaching.Owing in containing the leaching of nickel ore concentrate sulfuric acid, can produce the solution of a large amount of sulfur acid nickel, the effect of therefore low-cost recovery nickel technology in the industrial application that concentrate sulfuric acid leaches is better.In the further embodiment of the present invention, described nickel 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 nickel 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, cobalt, chromium thus, not only can reclaim compositions such as iron, copper, cobalt, chromium, and reclaim the nickel 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 nickel sulfate solution, generate the precipitation of larger particle, thereby separate easilier with the precipitation nickel 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 nickel sulfate solution and calcium oxide and/or calcium hydroxide reaction obtain calcium sulfate and nickel hydroxide, separating calcium sulphate and nickel 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 nickel hydroxide is washed and/or drying, can improve the purity of institute's separation of hydrogen nickel oxide like this, and be convenient to prolonged preservation.
In one embodiment of the invention, further comprise with separating the nickel hydroxide that obtains and produce the nickel goods, can utilize further nickel hydroxide like this, improve the economic value added that reclaims nickel 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 nickel that reclaims from nickel sulfate solution of first embodiment of the invention;
Fig. 2 is the schema of the method for nickel that reclaims from nickel sulfate solution of second embodiment of the invention;
Fig. 3 is the schema of the method for nickel that reclaims from nickel sulfate solution of third embodiment of the invention;
Fig. 4 is the schema of the method for nickel that reclaims from nickel sulfate solution of fourth embodiment of the invention;
Fig. 5 is the schema of the method for nickel that reclaims from nickel 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 nickel that reclaims of first embodiment of the invention from nickel sulfate solution.As shown in Figure 1, at first calcium oxide and/or calcium hydroxide are mixed with calcium sulfate as crystal seed.Then add nickel sulfate solution in resulting mixture, to generate calcium sulfate precipitation and nickel hydroxide precipitate, its reaction that mainly takes place is:
NiSO
4+Ca(OH)
2＝CaSO
4+Ni(OH)
2，
Last separating calcium sulphate and nickel hydroxide.
As mentioned above, single nickel salt in the nickel sulfate solution and calcium hydroxide reaction generate calcium sulfate precipitation and nickel hydroxide precipitate.Yet the particle of calcium sulfate precipitation and nickel hydroxide precipitate is all very little, and the granularity difference is smaller, and more specifically, calcium sulfate precipitation is a crystalline form, and nickel hydroxide is a gel, and nickel hydroxide is coated on the calcium sulfate, so the two is difficult to separate.In addition, when single nickel salt and calcium hydroxide reacted, the formation of nickel hydroxide precipitate 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 single nickel salt and calcium hydroxide react, contain calcium sulfate as crystal seed, therefore, when single nickel salt 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, is convenient to separating between follow-up calcium sulfate and the nickel hydroxide precipitate thus.
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 nickel sulfate solution is joined calcium oxide and/or calcium hydroxide and mixing as the calcium sulfate of crystal seed, then nickel sulfate solution is added and for example splash in the described mixture, can further improve the granularity of the calcium sulfate precipitation of the efficient of reaction and generation like this.
With reference to figure 2, in one embodiment of the invention, as the calcium sulfate of crystal seed be to use calcium sulfate precipitation that alkali-metal vitriol and calcium oxide and/or calcium hydroxide reaction generated, to separate the back resulting.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, the alkali-metal vitriol of use is sodium sulfate, because the cost of sodium sulfate is low, the sodium hydroxide that generates 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 nickel hydroxide, separating calcium sulphate and nickel hydroxide, then the calcium sulfate after separating is carried out obtaining after the classification washing by nickel 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 saved to produce and produced this.For example, can in the part of sulfuric acid nickel solution, add a certain amount of calcium oxide and/or calcium hydroxide earlier, obtain calcium sulfate and nickel hydroxide precipitate, from this reaction system, isolate calcium sulfate and nickel hydroxide then, 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 nickel 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 nickel sulfate solution as crystal seed, also the calcium sulfate nickel 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 nickel sulfate solution as crystal seed, the contriver finds to adopt this method can improve efficient at follow-up single nickel salt and calcium hydroxide reaction, further facilitates later separation nickel hydroxide and calcium sulfate.
Milk of lime is mixed with nickel sulfate solution, and stir, thereby single nickel salt and milk of lime react, and have generated throw out calcium sulfate and nickel hydroxide, principal reaction is NiSO
4+ Ca (OH)
2=Ni (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 nickel 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 nickel hydroxide.Therefore can easily calcium sulfate be separated with nickel hydroxide according to two kinds of sedimentary granular size differences.
In addition, in one embodiment of the invention, in order to obtain the higher nickel hydroxide of purity, and prolonged preservation, isolated nickel hydroxide is washed and/or dry.Washings can adopt deionized water, can prevent that like this nickel hydroxide suspension from flocculating.Through after static, the sedimentation, remove the supernatant liquor of cumulative volume about 50% at nickel hydroxide slurries that separation is obtained, promptly can obtain denseer hydroxide slurry material, this slurry is through filtering, and can obtain nickeliferously more than 42%, and calcic is lower than 0.5% product.
With reference to figure 5, in one embodiment of the invention, separate the nickel hydroxide that obtains and to be used to prepare the nickel 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 nickel hydroxide) on surface through washing.In addition, resulting calcium sulfate can also be used to prepare sulfuric acid and cement.
The source of nickel sulfate solution is not subjected to any restriction in the present invention, as long as contain single nickel salt in its solution.With reference to figure 3, in one embodiment of the invention, nickel sulfate solution is to contain the leach liquor of nickel ore concentrate or the leaching of nickel-containing material sulfuric acid through the solution after purifying.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 single nickel salt not only is untreated as waste liquid, and nickel 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, nickel sulfate solution is to contain nickel ore concentrate or the nickel-containing material sulphuric leachate solution through obtaining after purifying, and promptly reclaims other compositions in (removals) leach liquor earlier, reclaims the interior nickel that exists with the single nickel salt form of waste liquid again.For example, " purification " can be at least a metal of removing in the sulphuric leachate, for example iron, copper, cobalt 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 nickel from nickel 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 nickel sulfate solution, to generate calcium sulfate precipitation and nickel hydroxide precipitate; And
C) separating calcium sulphate and nickel hydroxide.
2. the method that from nickel sulfate solution, reclaims nickel according to claim 1, it is characterized in that, the mixture of calcium oxide and/or calcium hydroxide and calcium sulfate is mixed with nickel sulfate solution comprise nickel 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 nickel from nickel sulfate solution according to claim 1 is characterized in that, described nickel sulfate solution is the leach liquor that contains nickel ore concentrate or the leaching of nickel-containing material sulfuric acid.
4. the method that reclaims nickel from nickel sulfate solution according to claim 3 is characterized in that, described nickel sulfate solution is the solution of described leach liquor through obtaining after purifying.
5. the method that reclaims nickel from nickel 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 nickel from nickel 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 nickel from nickel sulfate solution according to claim 6 is characterized in that described alkali-metal vitriol is sodium sulfate.
8. the method that from nickel sulfate solution, reclaims nickel according to claim 1, it is characterized in that, as the calcium sulfate of crystal seed by nickel sulfate solution and calcium oxide and/or calcium hydroxide reaction obtain calcium sulfate and nickel hydroxide, separating calcium sulphate and nickel hydroxide, and isolating calcium sulfate washed after obtain.
9. the method that reclaims nickel from nickel sulfate solution according to claim 1 is characterized in that, further comprises isolated nickel hydroxide is washed and drying.
10. the leaching method of nickel-containing ore according to claim 1 is characterized in that, further comprises with separating the nickel hydroxide that obtains producing the nickel goods.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200810238840A CN101760635A (en) | 2008-12-02 | 2008-12-02 | Method for recovering nickel from nickel sulfate solution |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200810238840A CN101760635A (en) | 2008-12-02 | 2008-12-02 | Method for recovering nickel from nickel sulfate solution |
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| CN101760635A true CN101760635A (en) | 2010-06-30 |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN103397185A (en) * | 2013-06-24 | 2013-11-20 | 中南大学 | Method for calcium removal during iron precipitation of nickel sulfate solution containing iron and free sulfuric acid |
| CN103993175A (en) * | 2014-05-23 | 2014-08-20 | 中国恩菲工程技术有限公司 | Method for treating cobalt nickel sulfate solution |
| AU2013238535B2 (en) * | 2012-03-29 | 2016-06-16 | Sumitomo Metal Mining Co., Ltd. | Method for producing high-purity nickel sulfate |
| CN103993175B (en) * | 2014-05-23 | 2016-11-30 | 中国恩菲工程技术有限公司 | The processing method of nickel sulfate cobalt liquor |
-
2008
- 2008-12-02 CN CN200810238840A patent/CN101760635A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU2013238535B2 (en) * | 2012-03-29 | 2016-06-16 | Sumitomo Metal Mining Co., Ltd. | Method for producing high-purity nickel sulfate |
| US9702023B2 (en) | 2012-03-29 | 2017-07-11 | Sumitomo Metal Mining Co., Ltd. | Method for producing high-purity nickel sulfate |
| 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 |
| CN103397185A (en) * | 2013-06-24 | 2013-11-20 | 中南大学 | Method for calcium removal during iron precipitation of nickel sulfate solution containing iron and free sulfuric acid |
| CN103993175A (en) * | 2014-05-23 | 2014-08-20 | 中国恩菲工程技术有限公司 | Method for treating cobalt nickel sulfate solution |
| CN103993175B (en) * | 2014-05-23 | 2016-11-30 | 中国恩菲工程技术有限公司 | The processing method of nickel sulfate cobalt liquor |
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Application publication date: 20100630 |