CN101760616B - Leaching method of cobalt-containing ore - Google Patents
Leaching method of cobalt-containing ore Download PDFInfo
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- CN101760616B CN101760616B CN2008102388463A CN200810238846A CN101760616B CN 101760616 B CN101760616 B CN 101760616B CN 2008102388463 A CN2008102388463 A CN 2008102388463A CN 200810238846 A CN200810238846 A CN 200810238846A CN 101760616 B CN101760616 B CN 101760616B
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Abstract
The invention provides a leaching method of cobalt-containing ore, comprising the following steps: A) mixing the cobaltic ore with sulfuric acid solution and performing sulfuric acid leaching to obtain leaching solution containing cobaltous sulfate; B) purifying the leaching solution to obtain cobaltous sulfate solution; C) mixing the cobaltous sulfate solution with calcium oxide and / or calciumhydroxide and calcium sulfate which is used as the seed crystal to produce calcium sulfate precipitation and calcium hydroxide precipitation; and D) separating the calcium sulfate from the calcium hydroxide. The invention can recover metallic elements from the cobaltic ore with low cost and low pollution, thereby realizing the recycle of resources, lowering the production cost and lightening the environmental pollution.
Description
Technical field
The present invention relates to wet method smelting process, especially relate to leaching method of cobalt-containing ore.
Background technology
Ore smelting is traditionally undertaken by pyrometallurgical smelting process.Developed wet process smelting technique in recent years.Because hydrometallurgy can reduce the pollution to environment effectively, and can be suitable for multiple different ore deposit, therefore replace pyrometallurgical smelting just gradually.
Present wet method smelting process adopts sulphuric acid solvent extraction method more, the multiple metallic element that can leach in the ore to be contained.If can not reclaim, will be great waste, and some composition in the leach liquor also may damage to human body to these metallic elements.When for example cobalt-containing ore being leached, can produce the solution that contains rose vitriol in a large number, traditional treatment process is that the solution that will contain rose vitriol carries out heating evaporation, obtains the rose vitriol crystal.But the shortcoming of this treatment process is the cost height, and efficient is low, need to consume a large amount of energy, and resulting rose vitriol crystalline purity is low.
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, thus one object of the present invention is to propose the low-cost leaching method that a kind of granularity that can increase calcium sulfate better reclaims the cobalt-containing ore of cobalt.
Leaching method of cobalt-containing ore according to the embodiment of the invention may further comprise the steps: A) cobalt-containing ore is mixed with sulphuric acid soln and carry out the sulfuric acid leaching to obtain containing the leach liquor of rose vitriol; B) described leach liquor is purified obtain cobalt sulfate solution; C) mix with described cobalt sulfate solution and calcium oxide and/or calcium hydroxide and as the calcium sulfate of crystal seed, to generate calcium sulfate precipitation and cobaltous hydroxide precipitation; And D) separating calcium sulphate and cobaltous hydroxide.
The cobalt-containing ore leaching method can reclaim the metallic element in the cobalt-containing ore according to an embodiment of the invention.Simultaneously owing to the calcium sulfate that exists in the reaction system of rose vitriol and calcium hydroxide as crystal seed, therefore, the granularity of the calcium sulfate that generates in can the augmenting response process, thereby help later separation calcium sulfate and cobaltous hydroxide precipitation, therefore, the present invention can reclaim metallic element with low-cost, oligosaprobic mode from cobalt-containing ore, reach the recycling of resource, and reducing production costs alleviates environmental pollution.。
In the leaching method of cobalt-containing ore of one embodiment of the present of invention, described cobalt sulfate solution and calcium oxide and/or calcium hydroxide and mix as the calcium sulfate of crystal seed and to comprise at first calcium oxide and/or calcium hydroxide are mixed with calcium sulfate as crystal seed then join described cobalt sulfate solution in the mixture of calcium oxide and/or calcium hydroxide and calcium sulfate.The present inventor finds at first calcium oxide and/or calcium hydroxide are mixed with calcium sulfate as crystal seed, add cobalt sulfate solution again, can improve the reaction efficiency of follow-up rose vitriol and calcium hydroxide, and can further improve difference on calcium sulfate and the cobaltous hydroxide precipitation granularity, and then can improve separation efficiency.
In cobalt-containing ore leaching method according to an embodiment of the invention, described sulfuric acid leaches to the oxygen enrichment normal pressure leaches or the leaching of oxygen enrichment high pressure, can promote the efficient that sulfuric acid leaches like this.
In cobalt-containing ore leaching method according to an embodiment of the invention, the described ore that contains cobalt is a cobalt concentrate.Owing in the concentrate sulfuric acid that contains cobalt leaches, 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 cobalt concentrate sulfuric acid leaches is better.
In the cobalt-containing ore leaching method of one embodiment of the present of invention, described purification comprises at least a in the iron removed in the leach liquor, copper, the nickel, thus, not only can reclaim compositions such as iron, copper, nickel, and reclaimed the cobalt in the ore, both reduced pollution, again recycle resource.
In cobalt-containing ore leaching method according to an embodiment of the invention, as the calcium sulfate of crystal seed by alkali-metal vitriol and calcium oxide and/or calcium hydroxide reaction preparation.The resulting like this calcium sulfate as crystal seed can make easier being attached on it of calcium sulfate in the cobalt sulfate solution, generates the precipitation of larger particle, thus easier and cobaltous hydroxide precipitate and separate.
In further embodiment, described alkali-metal vitriol is sodium sulfate, can save cost like this.
In cobalt-containing ore leaching method according to an embodiment of the invention, as the calcium sulfate of crystal seed is to obtain calcium sulfate and cobaltous hydroxide, separating calcium sulphate and cobaltous hydroxide then by cobalt sulfate solution and calcium oxide and/or calcium hydroxide reaction, and isolating calcium sulfate is washed acquisition.Can save alkali-metal vitriol like this, save cost.
In cobalt-containing ore leaching method according to an embodiment of the invention, further comprise with separating the cobaltous hydroxide that obtains and make the cobalt goods, can utilize further cobaltous hydroxide like this, improve the economic worth that reclaims.
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 leaching method of cobalt-containing ore according to an embodiment of the invention;
Fig. 2 is the schema of leaching method of cobalt-containing ore according to another embodiment of the present invention;
Fig. 3 is the schema of leaching method of cobalt-containing ore according to another embodiment of the present invention;
Fig. 4 is the schema of leaching method of cobalt-containing ore according to another embodiment of the present invention;
Fig. 5 is the schema of leaching method of cobalt-containing ore according to another embodiment of the present 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.
In addition, term " valuable metal " (valuable metals) is meant in the raw material of extracting metals in the present invention, except that main metal, has other metals of recovery value.In general, whether a certain metal has recovery value, depend on the use value of this metal, the expense and the commodity price thereof of recovery needs, for example, germanium in the plumbous zinc ore is not before semi-conductor industry is risen, the value that reclaims is also little, and has become to have very much the metal of recovery value after the 1950's.Main metal content is lower in the heavy metallic mineral that has, and not necessarily has extraction value, but other valuable metals more for a long time, takes all factors into consideration, and then has extraction value.Sometimes, according to certain concrete social condition such as war etc., and when certain metal had specific demand,, also reclaim possibly even temporarily not too reasonable economically.In a word, the notion that " valency is arranged " is not unalterable in the present invention.
Fig. 1 shows the schema of leaching method of cobalt-containing ore according to an embodiment of the invention.According to shown in Figure 1, at first cobalt-containing ore joined and carry out the sulfuric acid leaching in the sulphuric acid soln to obtain containing the leach liquor of rose vitriol; Described leach liquor purified obtain cobalt sulfate solution; Then, mix with resulting cobalt sulfate solution and calcium oxide and/or calcium hydroxide and as the calcium sulfate of crystal seed, to generate calcium sulfate precipitation and cobaltous hydroxide precipitation, the principal reaction that is taken place is:
CoSO
4+Ca(OH)
2＝Co(OH)
2↓+CaSO
4↓；
At last, separating calcium sulphate and cobaltous hydroxide.
As previously mentioned,, leach in the leach liquor, and can reclaim multiple valuable metal, for example iron, copper, nickel by purifying by the metallic element in the cobalt-containing ore is leached by sulfuric acid.In addition, as mentioned above, after adding calcium oxide and/or calcium hydroxide, 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, if do not add calcium sulfate as crystal seed in advance in cobalt sulfate solution, cobaltous hydroxide has limited the further increase of calcium sulfate granularity, thereby has further increased separating difficulty.According to embodiments of the invention, owing to exist as crystalline calcium sulfate in the reaction system of rose vitriol and calcium hydroxide, calcium sulfate can be with CaSO
4XH
2The crystallized form of O (x is about 2/3) is precipitated out, therefore react in the sedimentary process that generates calcium sulfate and cobaltous hydroxide at rose vitriol and calcium hydroxide, calcium sulfate precipitation can be formed on the crystal seed, thereby the granularity of calcium sulfate precipitation can further increase, promptly form 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.
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 principal reaction that is taken place is:
Na
2SO
4+Ca(OH)
2＝CaSO
4+2NaOH。The contriver finds that the calcium sulfate that uses this method to obtain can obviously increase the granularity of calcium sulfate 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, therefore when can being convenient to separation of hydrogen sodium oxide and calcium sulfate, has also reduced cost.
With reference to figure 3, 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, obtain after the calcium sulfate after separating is washed then 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 saved to produce and produced this.For example, can to being mixed with calcium oxide and/or calcium hydroxide, the part of sulfuric acid cobalt liquor obtain calcium sulfate and cobaltous hydroxide precipitation earlier, from this solution, isolate calcium sulfate and cobaltous hydroxide then, and the calcium sulfate precipitation that obtains is washed and the dry calcium sulfate that obtains as crystal seed.
In addition, as mentioned above, at the beginning of technological process, the calcium sulfate of buying from market can be mixed the crystal seed that uses after the calcium sulfate that obtains by reaction, separation just can be used as then with cobalt sulfate solution as crystal seed.
In the present invention, can add calcium oxide (unslaked lime), also can add calcium hydroxide (white lime), also can add the mixture of the two.Particularly, 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 understood by those skilled in the art that promptly and milk of lime can be joined in the cobalt sulfate solution, also cobalt sulfate solution can be joined in the milk of lime.With reference to figure 5, in one embodiment of the invention, cobalt sulfate solution and calcium oxide and/or calcium hydroxide and to mix as the calcium sulfate of crystal seed be by at first calcium oxide and/or calcium hydroxide being mixed with calcium sulfate as crystal seed add in resulting mixture then that cobalt sulfate solution carries out.The contriver finds at first calcium oxide and/or calcium hydroxide are mixed with calcium sulfate as crystal seed, add cobalt sulfate solution again, can improve the reaction efficiency of follow-up rose vitriol and calcium hydroxide, and can further improve difference on calcium sulfate and the cobaltous hydroxide precipitation granularity, and then can improve separation efficiency.In a further embodiment, cobalt sulfate solution is added drop-wise in calcium oxide and/or calcium hydroxide and the mixture as the calcium sulfate of crystal seed, can improve whole effect so widely.
Because it is big that the granularity of the size ratio cobaltous hydroxide of calcium sulfate is wanted, and owing to the calcium sulfate that in the reaction system of rose vitriol and calcium hydroxide, exists as crystal seed, with do not add crystal seed and compare, therefore the granulometric facies of the calcium sulfate precipitation that is generated can further increase and can easily calcium sulfate be separated with cobaltous hydroxide according to two kinds of sedimentary granular size differences for the granularity of cobaltous hydroxide.
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 dry.Washings can adopt deionized water, can prevent that like this cobaltous hydroxide suspension from flocculating.
With reference to figure 4, 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 3, 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.
The sulfuric acid extract technology that is adopted among the present invention is not subjected to any restriction.For example, leaching can be leached or the leaching of oxygen enrichment high pressure for the oxygen enrichment normal pressure.Leaching process comprises that fine grinding contains cobalt concentrate; Carry out pulp with the cobalt concentrate that contains of sulphuric acid soln after to fine grinding; Concentrate after the pulp joined leach in the container, wherein leaching temperature in the container, to be controlled to be 90 ℃-100 ℃, pressure be normal pressure, and aerating oxygen leaches so that carry out the oxygen enrichment normal pressure in leaching container simultaneously.
Term " purification " can be to remove at least a in iron in the sulphuric leachate, copper, the nickel in the present invention, 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 (8)
1. leaching method of cobalt-containing ore may further comprise the steps:
A) cobalt-containing ore is mixed with sulphuric acid soln carry out acidleach to obtain the leach liquor of sulfur acid cobalt;
B) described leach liquor is purified obtain cobalt sulfate solution;
C) at first calcium oxide and/or calcium hydroxide are mixed with calcium sulfate as crystal seed, then described cobalt sulfate solution is joined in the mixture of calcium oxide and/or calcium hydroxide and calcium sulfate, to generate calcium sulfate precipitation and cobaltous hydroxide precipitation; And
D) separating calcium sulphate and cobaltous hydroxide.
2. leaching method of cobalt-containing ore according to claim 1 is characterized in that, described acidleach is leached for the oxygen enrichment normal pressure or the oxygen enrichment high pressure leaches.
3. leaching method of cobalt-containing ore according to claim 1 is characterized in that, the described ore that contains cobalt is a cobalt concentrate.
4. leaching method of cobalt-containing ore according to claim 3 is characterized in that, described purification comprises at least a in the iron removed in the leach liquor, copper, the nickel.
5. leaching method of cobalt-containing ore according to claim 1 is characterized in that, as the calcium sulfate of crystal seed by alkali-metal vitriol and calcium oxide and/or calcium hydroxide reaction preparation.
6. leaching method of cobalt-containing ore according to claim 5 is characterized in that described vitriol is sodium sulfate.
7. leaching method of cobalt-containing ore according to claim 1, it is characterized in that, as the calcium sulfate of crystal seed is to 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 is washed acquisition.
8. leaching method of cobalt-containing ore according to claim 1 is characterized in that, further comprises with separating the cobaltous hydroxide that obtains making the cobalt goods.
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| CN101760616B true CN101760616B (en) | 2011-08-10 |
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| 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 |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6391089B1 (en) * | 2000-11-29 | 2002-05-21 | Walter Curlook | Acid leaching of nickel laterite ores for the extraction of their nickel and cobalt values |
| CN1392902A (en) * | 2000-09-18 | 2003-01-22 | 英科有限公司 | Recovery of nickel and cobalt values from sulfidic flotation concentrate by chloride assisted oxidative pressure leaching in sulfuric acid |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1392902A (en) * | 2000-09-18 | 2003-01-22 | 英科有限公司 | Recovery of nickel and cobalt values from sulfidic flotation concentrate by chloride assisted oxidative pressure leaching in sulfuric acid |
| US6391089B1 (en) * | 2000-11-29 | 2002-05-21 | Walter Curlook | Acid leaching of nickel laterite ores for the extraction of their nickel and cobalt values |
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