CN101629247A - Combined leaching process of white alloy and heterogenite - Google Patents

Abstract

The invention relates to a combined leaching method of white alloy and heterogenite, which comprises the following steps: respectively crashing heterogenite and white alloy and screening by a 80-mesh sieve, carrying out mixed pulping according to the mol ratio that [n (Co)] heterogenite : [n (Cu)*2+n (Fe)] white alloy is more than or equal to 1, concentrating by a thickener till the pulp density is more than 60 percent, and then carrying out acid leaching; regulating the pH value of the pulp to be less than 1.5 by adding 98 percent of sulfuric acid into the obtained pulp, then adding Fe<2+> catalyst, leaching under the conditions that the stirring rotation speed is 500-800r/min, the leaching temperature is more than 70 DEG C, and the leaching time is 4-9h so that the Fe<2+> density in the pulp reaches 1.0-3.0g/L; considering the density as a leaching finishing point when cobalt in dregs is less than 0.3 percent; directly adding sodium chlorate as oxidant that is half of the residual Fe<2+> on the mass into dreg liquid mixture so as to oxidize the residual Fe<2+> into Fe<3+>, then adding sodium carbonate to regulate the pH value that is equal to 2.5-3.5 and carrying out iron precipitation, and then carrying out solid-liquid separation to obtain the leaching liquid. The invention is unnecessary to use oxidant and a great deal of reducing agent with higher economic value, and has less pollution and high benefits.

Description

A kind of white metal and heterogenite combined leaching process

Technical field

The present invention relates to the leaching method of cobalt ore, relate in particular to the associating catalysis leaching method of heterogenite and white metal.

Background technology

Cobalt is a kind of application metal more widely, can be used for alloying, permanent magnet, Precise Alloy, accumulate material etc.

The extract technology of heterogenite is typical hydrometallurgical processes, and at normal pressure, through the effect of reductive agent, cobalt just can be leached certain acidity condition down.The conventional acid of using is sulfuric acid, and reductive agent is S-WAT or sulfurous gas.This working method all compares the close friend to equipment requirements and environment, is handled producer by most heterogenite and adopts.

But continuous exploitation along with world's cobalt ore; the higher-grade cobalt ore constantly reduces; various countries, cobalt ore main product ground are for to the protection of national resource and be the create more jobs consideration of chance of this country in addition; the increasing pretreated one-tenth of cobalt ore just is allowed to outlet after containing the higher white metal of cobalt copper, just seems very urgent so seek the white metal treatment process of economic environmental protection.

The leaching of white metal and the leaching condition of heterogenite are completely contradicted, and the copper of white metal the inside need could be leached in oxidizing atmosphere under the acidic conditions.What be as oxygenant usually has air, oxygen, chlorine, sodium chlorate, a Fe ³⁺, Cu ²⁺Deng.Efficient is not high when being oxygenant with the air, and cost is too big when being oxygenant with oxygen, and severe operational environment and chlorine have certain danger when being oxygenant with chlorine, faces the too big difficult problem of cost when being oxygenant with the sodium chlorate equally, separately with Fe ³⁺Or Cu ²⁺Face lot of F e in the leach liquor during for oxygenant again ²⁺Or Cu ⁺The problem that needs oxidized processing.

Summary of the invention

The purpose of this invention is to provide a kind of white metal and heterogenite and unite the method for leaching, do not need additional oxidizer in the leaching process, also do not need a large amount of reductive agents simultaneously.

The technical solution used in the present invention is:

A kind of white metal and heterogenite are united the method for leaching, it is characterized in that comprising following steps:

Step 1, with heterogenite and white metal separated pulverizing and cross 80 mesh sieves, [n (Co)] then in molar ratio _Heterogenite: [n (Cu) * 2+n (Fe)] _{White metal}〉=1 batching is also carried out mixed pulp, carries out acidity and leach after thickener concentrates pulp density＞60%;

Step 2, employing catalyzer+sulfuric acid system leach: add in the ore pulp that makes earlier and add Fe after 98% sulfuric acid is regulated pH＜1.5 ²⁺Catalyzer leaches under mixing speed 500-800r/min, extraction temperature＞70 ℃, the condition of extraction time 4-9h, makes Fe in the ore pulp ²⁺Concentration reaches 1.0-3.0g/L, is considered as leaching terminal point during cobalt in recording slag＜0.3%;

Step 3, the heavy iron of employing goethite process: the slag liquid mixture that obtains in step 2 directly adds 0.5 times of remaining Fe ²⁺The oxygenant chloric acid sodium of quality is with residual Fe ²⁺Be oxidized to Fe ³⁺, add soda ash then and regulate pH=2.5-3.5 and sink iron;

Step 4, carry out solid-liquid separation, obtain containing the leach liquor of valuable metals such as Co, Cu, Mn, Ni, and send follow-up removal of impurities operation.

Fe in the step 2 of the present invention ²⁺Catalyzer be FeSO ₄Or directly adding iron powder, described 98% vitriol oil is disposable continuous adding.

Among the present invention white metal and heterogenite mixed in certain proportion through pulverize slurrying handle after particle size diameter less than 80 target standards, slurrying concentration＞60%, regulate pH＜1.5 to wherein directly adding 98% sulfuric acid, under the sour environment in the white metal cobalt come out by acidleach, the iron in the white metal also can be with Fe under the effect of acid ²⁺Form enter solution.At Fe ²⁺Effect under in the heterogenite in cobalt and the white metal copper leached by catalysis.Because heterogenite is excessive, the most iron in the solution finally can be with Fe ³⁺Form exist, in order to guarantee the leaching effect of heterogenite, need to replenish suitable Fe ²⁺, make Fe in the solution ²⁺Keep between the 1.0-3.0g/L concentration.Cobalt contents in slag＜0.3% is considered as leaching terminal point.Add very a spot of oxygenant chloric acid sodium then with part Fe remaining in the solution ²⁺Be oxidized to Fe ³⁺, add-on is remaining Fe ²⁺0.5 times of quality.Regulator solution pH=2.5-3.5 makes Fe ³⁺Form post precipitation with pyrrhosiderite filters together with insoluble slag, obtains containing the leach liquor of valuable metals such as cobalt, copper, manganese, nickel.

The blending ratio of heterogenite and white metal is determined as follows among the present invention: make mol ratio [n (Co)] _Heterogenite: [n (Cu) * 2+n (Fe)] _{White metal}〉=1.

Catalyzer among the present invention is Fe ²⁺, the mechanism of action is Fe ²⁺The cobalt that reduction is leached in the heterogenite generates Fe ³⁺, Fe ³⁺The copper that oxidation is leached in the white metal generates Fe ²⁺

Among the present invention the blending ratio of heterogenite and white metal determine to have certain elasticity, along with the increase of above-mentioned mol ratio, for the high leaching yield that guarantees heterogenite just needs to increase Fe ²⁺Input amount.What leach reaction in this case is the process that cobalt is leached simultaneously in copper and the heterogenite in the white metal in earlier stage, has just entered Fe after the white metal leaching process finishes ²⁺To the reductibility leaching process of surplus water cobalt ore, this moment Fe ²⁺That serve as is the role of reductive agent, so can add other reductive agent such as Na in the later stage of leaching ₂SO ₃Replace Fe ²⁺Effect, the conventional reduction leaching process of this and heterogenite is the same.

Mixing speed 500-800r/min among the present invention, extraction temperature＞70 ℃, extraction time 4-9h.

Should be noted that: the content that the present invention forgave is the leaching method of heterogenite and white metal, does not comprise the purification that equipment in the leaching process and leach liquor are follow-up and the preparation of product.

Heterogenite white metal combined leaching process of the present invention has following advantage: the conglomeration in certain proportion of heterogenite and white metal is leached, with Fe ²⁺Be catalyzer, do not need higher oxygenant of economic cost such as oxygen, chlorine, sodium chlorate etc., also do not need a large amount of reductive agents such as SO simultaneously ₂, Na ₂SO ₃Deng, operational condition is good, and environmental pollution is little.Can utilize conventional heterogenite pickling equipment to carry out the processing of white metal, handiness is big, and hardware investment is few.

Embodiment

Embodiment 1

Heterogenite white metal combined leaching process of the present invention, with heterogenite and white metal with mol ratio [n (Co)] _Heterogenite: [n (Cu) * 2+n (Fe)] _{White metal}=1.08 mixed crushing and water-adding slurrying obtains the ore pulp of water-content 40%.Regulate pH to 1.4 to the vitriol oil that wherein directly adds 98%, mixing speed 600r/min, steam heat to 70 ℃, react after 4 hours to wherein adding the FeSO that concentration is 1mol/L ₄Solution, Fe in the regulator solution ²⁺Concentration 1.0-3.0g/L scope, cobalt in the slag＜0.3%.In solution, add 0.5 times of remaining Fe ²⁺The sodium chlorate of quality continues to stir 2 hours after-filtration and obtains leach liquor.

Embodiment 2

Heterogenite white metal combined leaching process of the present invention, with heterogenite and white metal with mol ratio [n (Co)] _Heterogenite: [n (Cu) * 2+n (Fe)] _{White metal}=1.15 mixed crushing and water-adding slurrying obtains the ore pulp of water-content 30%.Regulate pH to 1.2 to the vitriol oil that wherein directly adds 98%, mixing speed 700r/min, steam heat to 75 ℃, react after 5 hours to wherein adding the FeSO that concentration is 1mol/L ₄Solution, Fe in the regulator solution ²⁺Concentration 1.0-3.0g/L scope, cobalt in the slag＜0.3%.In solution, add 0.5 times of remaining Fe ²⁺The sodium chlorate of quality continues to stir 2.5 hours after-filtration and obtains leach liquor.

Embodiment 3

Heterogenite white metal combined leaching process of the present invention, with heterogenite and white metal with mol ratio [n[n (Co)] _Heterogenite: [n (Cu) * 2+n (Fe)] _{White metal}=1.5 mixed crushing and water-adding slurrying obtains the ore pulp of water-content 35%.Regulate pH to 1.0 to the vitriol oil that wherein directly adds 98%, mixing speed 800r/min, steam heat to 85 ℃, react after 4 hours to wherein slowly adding straight iron powder, Fe in the regulator solution ²⁺Concentration 1.0-3.0g/L scope, cobalt in the slag＜0.3%.In solution, add 0.5 times of Fe ²⁺The sodium chlorate of quality continues to stir 4 hours after-filtration and obtains leach liquor.

Claims (2)

1, a kind of white metal and heterogenite are united the method for leaching, it is characterized in that comprising following steps:

Step 1, with heterogenite and white metal separated pulverizing and cross 80 mesh sieves, [n (Co)] then in molar ratio _Heterogenite: [n (Cu) * 2+n (Fe)] _{White metal}〉=1 batching is also carried out mixed pulp, carries out acidity and leach after thickener concentrates pulp density＞60%;

Step 2, employing catalyzer+sulfuric acid system leach: after in the ore pulp that makes, adding 98% sulfuric acid adjusting pH＜1.5 earlier, and adding Fe ²⁺Catalyzer leaches under mixing speed 500-800r/min, extraction temperature＞70 ℃, the condition of extraction time 4-9h, makes Fe in the ore pulp ²⁺Concentration reaches 1.0-3.0g/L, is considered as leaching terminal point during cobalt in recording slag＜0.3%;

Step 3, the heavy iron of employing goethite process: the slag liquid mixture that obtains in step 2 directly adds 0.5 times of remaining Fe ²⁺The oxygenant chloric acid sodium of quality is with residual Fe ²⁺Be oxidized to Fe ³⁺, add soda ash then and regulate pH=2.5-3.5 and sink iron;

Step 4, carry out solid-liquid separation, obtain containing the leach liquor of valuable metals such as Co, Cu, Mn, Ni, and send follow-up removal of impurities operation.

2, a kind of white metal according to claim 1 and heterogenite are united the method for leaching, it is characterized in that Fe in the step 2 ²⁺Catalyzer is FeSO ₄Or directly adding iron powder, described 98% vitriol oil is disposable continuous adding.