CN101760615A - Leaching method of copper-containing ore - Google Patents

Leaching method of copper-containing ore Download PDF

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Publication number
CN101760615A
CN101760615A CN200810238845A CN200810238845A CN101760615A CN 101760615 A CN101760615 A CN 101760615A CN 200810238845 A CN200810238845 A CN 200810238845A CN 200810238845 A CN200810238845 A CN 200810238845A CN 101760615 A CN101760615 A CN 101760615A
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China
Prior art keywords
copper
calcium
ore
hydroxide
leaching
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CN200810238845A
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Chinese (zh)
Inventor
王魁珽
刘金山
陆业大
高保军
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China ENFI Engineering Corp
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China ENFI Engineering Corp
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Priority to CN200810238845A priority Critical patent/CN101760615A/en
Publication of CN101760615A publication Critical patent/CN101760615A/en
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    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00Technologies related to metal processing
    • Y02P10/20Recycling

Abstract

The invention provides a leaching method of copper-containing ore, comprising the following steps: 1) mixing the coppery ore with sulfuric acid solution and performing the sulfuric acid leaching to obtain leaching solution which contains copper sulfate; 2) purifying the leaching solution to obtain copper sulfate solution; 3) mixing the copper sulfate solution with calcium oxide and/or calcium hydroxide and calcium sulfate which is used as the seed crystal to produce calcium sulfate precipitation and copper hydroxide precipitation; and 4) separating the calcium sulfate from the copper hydroxide. The invention can recover metallic elements in the coppery ore with low cost and low pollution, thereby realizing the recycle of resources, producing the calcium sulfate (plaster) incidentally, lowering production cost and reducing environmental pollution.

Description

Leaching method of copper-containing ore
Technical field
The present invention relates to wet method smelting process, especially relate to leaching method of copper-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 copper-containing ore being leached, can produce the solution that contains copper sulfate in a large number.Traditional treatment process is that the solution that will contain copper sulfate carries out heating evaporation, obtains copper sulfate 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 the purity of resulting copper sulfate crystal is low.
For example, Chinese patent CN 1041339 discloses a kind of treatment process of bluestone waste, and it comprises: be to be oxygenant with pressurized air, it is fed in the bluestone waste of chemical-copper-plating process, the oxidation ferrous iron becomes ferric iron, adds thermal effluent and adds NaCO simultaneously to 〉=90 ℃ 3(or NaOH) transfers the PH of solution to become acid (1.2-1.5) to add small amount of N aSO 4Na when reacting to increase +, fully stir then, generate ihleite, sedimentation at last after, reclaim(ed) sulfuric acid copper waste liquid.Because this technology adopts the operational path of pyroprocessing, and adopt strong acid environment to handle, therefore, mass consumption the energy, environment caused once more polluted, and because methods such as this process using calcinings, therefore to the requirement height of equipment, and then 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, 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 copper-containing ore of copper.
Leaching method of copper-containing ore according to the embodiment of the invention may further comprise the steps: A) copper-containing ore is mixed with sulphuric acid soln and carry out the sulfuric acid leaching to obtain containing the leach liquor of copper sulfate; B) described leach liquor is purified obtain copper-bath; C) mix with described copper-bath and calcium oxide and/or calcium hydroxide and as the calcium sulfate of crystal seed, to generate calcium sulfate precipitation and copper hydroxide precipitation; And D) separating calcium sulphate and copper hydroxide.
The copper-containing ore leaching method can reclaim the metallic element in the copper-containing ore according to an embodiment of the invention.Simultaneously owing to the calcium sulfate that exists in the reaction system of copper sulfate 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 copper hydroxide precipitation, therefore, the present invention can reclaim metallic element with low-cost, oligosaprobic mode from copper-containing ore, reach the recycling of resource, and attached product calcium sulfate (gypsum), reducing production costs alleviates environmental pollution.
In the leaching method that contains U.S. ore of one embodiment of the present of invention, described copper-bath 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 copper-bath 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 copper-bath again, can improve the reaction efficiency of follow-up copper sulfate and calcium hydroxide, and can further improve difference on calcium sulfate and the copper hydroxide precipitation granularity, and then can improve separation efficiency.
In copper-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 copper-containing ore leaching method according to an embodiment of the invention, described copper bearing ore is high copper-nickel concentrate.Owing in copper bearing concentrate sulfuric acid leaches, can produce the solution of a large amount of sulfur acid copper, the effect of therefore low-cost recovery process for copper in the industrial application that high copper-nickel concentrate sulfuric acid leaches is better.
In the copper-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, cobalt, the nickel, thus, not only can reclaim compositions such as iron, cobalt, nickel, and reclaimed the copper in the ore, both reduced pollution, again recycle resource.
In copper-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 copper-bath, generates the precipitation of larger particle, thus easier and copper hydroxide precipitate and separate.
In further embodiment, described alkali-metal vitriol is sodium sulfate, can save cost like this.
In copper-containing ore leaching method according to an embodiment of the invention, as the calcium sulfate of crystal seed is to obtain calcium sulfate and copper hydroxide, separating calcium sulphate and copper hydroxide then by copper-bath 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 copper-containing ore leaching method according to an embodiment of the invention, further comprise the copper hydroxide manufactured copper goods that obtain with separating, can utilize further copper 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 copper-containing ore according to an embodiment of the invention;
Fig. 2 is the schema of leaching method of copper-containing ore according to another embodiment of the present invention;
Fig. 3 is the schema of leaching method of copper-containing ore according to another embodiment of the present invention;
Fig. 4 is the schema of leaching method of copper-containing ore according to another embodiment of the present invention;
Fig. 5 is the schema of leaching method of copper-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 copper-containing ore according to an embodiment of the invention.According to shown in Figure 1, at first copper-containing ore joined and carry out the sulfuric acid leaching in the sulphuric acid soln to obtain containing the leach liquor of copper sulfate; Described leach liquor purified obtain copper-bath; Then, mix with resulting copper-bath and calcium oxide and/or calcium hydroxide and as the calcium sulfate of crystal seed, to generate calcium sulfate precipitation and copper hydroxide precipitation, the principal reaction that is taken place is:
CuSO 4+Ca(OH) 2=Cu(OH) 2↓+CaSO 4↓;
At last, separating calcium sulphate and copper hydroxide.
As previously mentioned,, leach in the leach liquor, and can reclaim multiple valuable metal by purifying by the metallic element in the copper-containing ore is leached by sulfuric acid, for example iron,, cobalt, nickel.In addition, as mentioned above, after adding calcium oxide and/or calcium hydroxide, copper sulfate in the copper-bath and calcium hydroxide reaction generate calcium sulfate precipitation and copper hydroxide precipitation.Yet the sedimentary particle of calcium sulfate precipitation and copper hydroxide is all very little, and the granularity difference is smaller, and more specifically, calcium sulfate precipitation is a crystalline form, and copper hydroxide is a gel, and copper 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 copper-bath, copper 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 in the reaction system of copper sulfate and calcium hydroxide as crystalline calcium sulfate, therefore react in the sedimentary process that generates calcium sulfate and copper hydroxide at copper sulfate 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 copper 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 copper hydroxide, separating calcium sulphate and copper hydroxide, obtain after the calcium sulfate after separating is washed then by copper-bath 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 copper solutions obtain calcium sulfate and copper hydroxide precipitation earlier, from this solution, isolate calcium sulfate and copper 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, 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 copper-bath 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 copper-bath, also copper-bath can be joined in the milk of lime.With reference to figure 5, in one embodiment of the invention, copper-bath 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 slurry as crystal seed add in resulting mixture then that copper-bath carries out.The contriver finds at first calcium oxide and/or calcium hydroxide are mixed with calcium sulfate as crystal seed, add copper-bath again, can improve the reaction efficiency of follow-up copper sulfate and calcium hydroxide, and can further improve difference on calcium sulfate and the copper hydroxide precipitation granularity, and then can improve separation efficiency.In a further embodiment, copper-bath 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 copper hydroxide of calcium sulfate is wanted, and owing to the calcium sulfate that in the reaction system of copper sulfate 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 copper hydroxide according to two kinds of sedimentary granular size differences for the granularity of copper hydroxide.
In addition, in one embodiment of the invention, in order to obtain the higher copper hydroxide of purity, and prolonged preservation, isolated copper hydroxide is washed and dry.Washings can adopt deionized water, can prevent that like this copper hydroxide suspension from flocculating.
With reference to figure 4, in one embodiment of the invention, separate the copper hydroxide that obtains and to be used to prepare brass work.
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 copper 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 copper ore concentrates; Carry out pulp with the copper ore concentrates 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.
In further embodiment of the present invention, copper-bath is a sulphuric leachate through the solution that obtains after purifying, and promptly reclaims other compositions in (removals) leach liquor earlier, and then reclaims the interior copper that exists with the copper sulfate form of waste liquid.Employed in the present invention term " purification " can be to remove at least a in iron in the sulphuric leachate, cobalt, the nickel, 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 (9)

1. leaching method of copper-containing ore may further comprise the steps:
A) copper-containing ore is mixed with sulphuric acid soln carry out acidleach to obtain the leach liquor of sulfur acid copper;
B) described leach liquor is purified obtain copper-bath;
C) mix with described copper-bath and calcium oxide and/or calcium hydroxide and as the calcium sulfate of crystal seed, to generate calcium sulfate precipitation and copper hydroxide precipitation; And
D) separating calcium sulphate and copper hydroxide.
2. leaching method of copper-containing ore according to claim 1, it is characterized in that, described copper-bath 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 copper-bath in the mixture of calcium oxide and/or calcium hydroxide and calcium sulfate.
3. leaching method of copper-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.
4. leaching method of copper-containing ore according to claim 1 is characterized in that, described copper bearing ore is high copper-nickel concentrate.
5. leaching method of copper-containing ore according to claim 4 is characterized in that, described purification comprises at least a in the iron removed in the leach liquor, cobalt, the nickel.
6. leaching method of copper-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.
7. leaching method of copper-containing ore according to claim 6 is characterized in that described vitriol is sodium sulfate.
8. leaching method of copper-containing ore according to claim 1, it is characterized in that, as the calcium sulfate of crystal seed is to obtain calcium sulfate and copper hydroxide, separating calcium sulphate and copper hydroxide by copper-bath and calcium oxide and/or calcium hydroxide reaction, and isolating calcium sulfate washs acquisition.
9. leaching method of copper-containing ore according to claim 1 is characterized in that, further comprises the copper hydroxide manufactured copper goods that obtain with separating.
CN200810238845A 2008-12-02 2008-12-02 Leaching method of copper-containing ore Pending CN101760615A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106381402A (en) * 2016-08-31 2017-02-08 四川省新源泰环保科技有限责任公司 Method for recovering germanium and copper from germanium-copper ore
CN110759526A (en) * 2019-10-28 2020-02-07 中国恩菲工程技术有限公司 Method for treating copper-containing waste liquid

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106381402A (en) * 2016-08-31 2017-02-08 四川省新源泰环保科技有限责任公司 Method for recovering germanium and copper from germanium-copper ore
CN110759526A (en) * 2019-10-28 2020-02-07 中国恩菲工程技术有限公司 Method for treating copper-containing waste liquid

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