CN104726701A - Method for leaching valuable metals in heterogenite - Google Patents
Method for leaching valuable metals in heterogenite Download PDFInfo
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- CN104726701A CN104726701A CN201510091939.8A CN201510091939A CN104726701A CN 104726701 A CN104726701 A CN 104726701A CN 201510091939 A CN201510091939 A CN 201510091939A CN 104726701 A CN104726701 A CN 104726701A
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- heterogenite
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Abstract
The invention relates to a method for leaching valuable metals in heterogenite. The method is characterized by comprising the following steps: crushing the heterogenite into particles with the particle size of more than or equal to 200 meshes, and adding a carbonaceous reducing agent, the weight of which is 1-30% of the heterogenite, to uniformly mix; dehydrating and roasting at 300-700 DEG C in a closed state; adding a leaching agent into a roasted and cooled material, introducing high-pressure gas to leach, heating, controlling the leaching temperature at 80-150 DEG C, controlling the stirring speed at 200-400 rpm, and controlling the leaching time for 30-200 min; and standing for 30 min after leaching, filtering, and washing filter residues by using hot water, wherein a filtrate and a washing solution are leachates containing a variety of valuable metals. According to the invention, the heterogenite difficult to dispose and utilize is used as the object; the valuable metals in the heterogenite are leached by taking dilute acid as the leaching agent through reducing and roasting pre-treatment, stirring and the like at a high temperature and high pressure; furthermore, separation of iron is realized synchronously; the method is simple in process and low in cost; and therefore, scale production can be realized.
Description
Technical field
The invention belongs to field of chemical metallurgical technology, relate to the heterogenite that the valuable element content such as the leaching method of valuable metal in a kind of heterogenite, particularly cobalt, copper, nickel, zinc, manganese is high, have remarkable use value.
Background technology
Cobalt is a kind of important strategy metal, expensive.As the functional element of lithium cell key, cobalt resource extremely lacks, and mostly belongs to low-grade complex associated minerals, reclaims for a long time as nickel, zinc metallurgical technology byproduct.Heterogenite is the cobalt resource that contains being mainly derived from the countries such as African Congo (Congo-Kinshasa), South Africa, Zambia, Guinea, containing chrysocolla, cobaltous oxide, hydroxyl water copper chlorine, cobaltic oxide, pyrolusite, zink sulphide, diaspore etc., current development of exploitation level is low, synthetical recovery is worth high.Heterogenite ore deposit is mutually complicated, and embedding cloth is fine, is generally 1.5 ~ 20% containing cobalt weight range, simultaneously the associated element such as cupric, nickel, manganese, zinc, iron, aluminium, calcium, magnesium, difficultly leaches difficult utilization, and heterogenite leaching method is associated with efficiency utilization containing cobalt resource and process costs.
The metallurgical leaching method of heterogenite conventional wet lay is for adding chemical reducing leaching, and leaching process pollutes large, the difficult control of processing parameter.
CN200910301216.0 discloses a kind of method of selective solvent extraction of heterogenite with full-wet-process, the vitriol oil or concentrated hydrochloric acid is adopted to make leaching agent, add the reductive agent containing ferrous ion, reducing leaching is carried out under temperature of reaction 60 ~ 90 DEG C of conditions, leach liquor oxidation reinforced dose of iron removal by oxidation, the method technique is more complicated, and cost is higher, there is the defect introducing impurity iron.
CN200910183820.8 discloses a kind of method that white metal and heterogenite combine leaching, catalyzer+sulfuric acid system is adopted to leach, adopt goethite process, the leach liquor containing valuable metals such as Co, Cu, Mn, Ni is obtained after solid-liquid separation, the method be white metal with heterogenite combine leaching, be not the single leaching method to heterogenite.
CN201010582776.0 discloses and carries out selective reduction acidleach heterogenite with sulfuric acid and reductive agent S-WAT, and leach liquor eddy flow electrical integration is got copper and cobalt indescribably, and after carrying cobalt, liquid returns for acidleach.The method needs interpolation S-WAT to do to leach auxiliary agent, easily sour decomposition reaction occurs in leaching process, has sulfur dioxide gas effusion phenomenon, causes environmental pollution.
Summary of the invention
The object of this invention is to provide the leaching method of valuable metal in a kind of heterogenite, method of the present invention can obtain the leach liquor containing valuable metals such as cobalt, copper, nickel, manganese, zinc simultaneously, leach liquor iron-holder is lower, alleviates the burden leaching postprocessing working procedures imurity-removal iron.
Method of the present invention is made up of following steps: broken heterogenite is to >=200 orders, and the carbonaceous reducing agent adding heterogenite quality 1 ~ 30% mixes; Dewater under air-tight state and 300 ~ 700 DEG C of temperature, roasting; Leaching agent is added cooled material, passes into high pressure gas and leach, heat and control extraction temperature 80 ~ 150 DEG C, stirring velocity 200 ~ 400rpm, extraction time 30 ~ 200min; Standing 30min after leaching completes, filters, uses hot wash filter residue, and filtrate and washings are the leach liquor containing multiple valuable metal.
Described carbonaceous reducing agent is activated carbon powder, coal dust or flour.
Described leaching agent is sulfuric acid or the hydrochloric acid of concentration 0.05 ~ 2.0M.
The liquid-solid ratio of the material after described leaching agent and roasting is 3 ~ 15: 1.
Described high pressure gas are nitrogen, the air or oxygen of 0.3 ~ 2.0MPa.
Reducing roasting of the present invention is that the heterogenite of fragmentation is added carbonaceous reducing agent, under air-tight state, the trivalent cobalt oxide not easily leached is reduced to the divalence cobalt oxide of easy acid leaching extraction in heterogenite.Adopt diluted acid to make leaching agent High Temperature High Pressure to leach, leaching auxiliary agent without the need to adding, utilizing the strengthening effect of High Temperature High Pressure, improve leaching velocity and the leaching yield of valuable metal.Under High Temperature High Pressure leaching condition, owing to there is the hydrolysis reaction of iron, ferriferous oxide belongs to the stable state not easily leached, and iron residues in slag and realizes mutually and being separated of the valuable metals such as cobalt, copper, nickel, manganese, zinc.
The present invention puts the difficult heterogenite utilized for object with difficulty, by reducing roasting pre-treatment, take diluted acid as leaching agent, by the strengthening such as High Temperature High Pressure, stirring means, leach the valuable metal in heterogenite, and synchronously realize the separation of iron, the method technique is simple, with low cost, can scale production be realized.
Embodiment
Embodiment 1
To containing cobalt 18%, copper 1.3%, nickel 0.2%, manganese 0.6%, the heterogenite of iron 2.0% is crushed to 200 orders, allocate 10% activated carbon powder into mix, put into resistance furnace, under 450 DEG C of temperature condition, roasting 3 hours, autoclave put into by cooled material, leaching agent is made with 0.2M sulfuric acid, it is 5: 1 that liquid-solid ratio controls, airtightly rear 130 DEG C are warming up to liquid heat, with rotating speed 400rpm stirred liq, pass into nitrogen, pressure is that 1.3MPa leaches, extraction time 180min, standing 30min after leaching completes, filter, with 80 DEG C of hot wash filter residues three times, filtrate and washings are for containing cobalt, copper, nickel, the leach liquor of the multiple valuable metal such as manganese, cobalt, copper, nickel, manganese, the leaching yield of iron is respectively 99.3%, 98.4%, 96.1%, 87.9%, 7.3%.
Embodiment 2
To containing cobalt 7%, copper 3.5%, nickel 0.8%, zinc 0.2%, the heterogenite of iron 1.6% is crushed to 200 orders, allocate 20% coal dust into mix, put into resistance furnace, under 550 DEG C of temperature condition, roasting 2 hours, autoclave put into by cooled material, leaching agent is made with 0.5M hydrochloric acid, it is 10: 1 that liquid-solid ratio controls, airtightly rear 140 DEG C are warming up to liquid heat, with rotating speed 400rpm stirred liq, pass into air, pressure is that 1.0MPa leaches, extraction time 150min, standing 30min after leaching completes, filter, with 90 DEG C of hot wash filter residues three times, filtrate and washings are for containing cobalt, copper, nickel, the leach liquor of the multiple valuable metal such as zinc, cobalt in process, copper, nickel, zinc, the leaching yield of iron is respectively 98.7%, 99.3%, 97.2%, 95.5%, 11.9%.
Embodiment 3
To containing cobalt 3.5%, copper 2.5%, nickel 1.9%, manganese 2.2%, zinc 1.2%, the heterogenite of iron 3.6% is crushed to 200 orders, allocate 20% flour into mix, put into resistance furnace, under 500 DEG C of temperature condition, roasting 2.5 hours, autoclave put into by cooled material, leaching agent is made with 0.8M sulfuric acid, it is 10: 1 that liquid-solid ratio controls, airtightly rear 120 DEG C are warming up to liquid heat, with rotating speed 400rpm stirred liq, pass into oxygen, pressure is that 1.1MPa leaches, extraction time 120min, standing 30min after leaching completes, filter, with 85 DEG C of hot wash filter residues three times, filtrate and washings are for containing cobalt, copper, nickel, zinc, the leach liquor of the multiple valuable metal such as manganese, cobalt in process, copper, nickel, manganese, zinc, the leaching yield of iron is respectively 95.1%, 97.0%, 94.8%, 93.2%, 98.8%, 19.4%.
Claims (5)
1. the leaching method of valuable metal in heterogenite, is characterized in that being made up of following steps: broken heterogenite is to >=200 orders, and the carbonaceous reducing agent adding heterogenite quality 1 ~ 30% mixes; Dewater under air-tight state and 300 ~ 700 DEG C of temperature, roasting; Leaching agent is added cooled material, passes into high pressure gas and leach, heat and control extraction temperature 80 ~ 150 DEG C, stirring velocity 200 ~ 400rpm, extraction time 30 ~ 200min; Standing 30min after leaching completes, filters, uses hot wash filter residue, and filtrate and washings are the leach liquor containing multiple valuable metal.
2. the leaching method of valuable metal in heterogenite according to claim 1, is characterized in that described carbonaceous reducing agent is activated carbon powder, coal dust or flour.
3. the leaching method of valuable metal in heterogenite according to claim 1, is characterized in that described leaching agent is sulfuric acid or the hydrochloric acid of concentration 0.05 ~ 2.0M.
4. the leaching method of valuable metal in the heterogenite according to claim 1 or 3, is characterized in that the liquid-solid ratio of the material after described leaching agent and roasting is 3 ~ 15: 1.
5. the leaching method of valuable metal in heterogenite according to claim 1, is characterized in that high pressure gas are nitrogen, the air or oxygen of 0.3 ~ 2.0MPa.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107779594A (en) * | 2017-08-31 | 2018-03-09 | 广东佳纳能源科技有限公司 | A kind of technique for being segmented reducing leaching Africa heterogenite |
| CN108048671A (en) * | 2017-11-24 | 2018-05-18 | 广东佳纳能源科技有限公司 | A kind of heterogenite leaching method of low cost |
| CN109338122A (en) * | 2018-11-06 | 2019-02-15 | 广东佳纳能源科技有限公司 | A kind of leaching method of heterogenite |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3361557A (en) * | 1965-03-22 | 1968-01-02 | R N Corp | Processes for direct reduction of ironbearing ores, slags and the like |
| CN101323909A (en) * | 2008-07-17 | 2008-12-17 | 东北大学 | Method of microwave selective reduction roasting-dilute acid leaching nickel oxide ore |
| CN101392320A (en) * | 2008-10-31 | 2009-03-25 | 东北大学 | Method for treating nickel-containing laterite by microwave reducing roasting-goethite precipitation conversion method |
| CN101509069A (en) * | 2009-03-30 | 2009-08-19 | 南通新玮镍钴科技发展有限公司 | Method for selective solvent extraction of heterogenite with full-wet-process |
| CN101629247A (en) * | 2009-07-31 | 2010-01-20 | 南通新玮镍钴科技发展有限公司 | Combined leaching process of white alloy and heterogenite |
| CN101994003A (en) * | 2010-12-10 | 2011-03-30 | 中南大学 | Process for selectively extracting copper and cobalt from heterogenite |
| WO2014000023A1 (en) * | 2012-06-29 | 2014-01-03 | Metaleach Limited | Method for recovering cobalt from cobalt-containing ores |
-
2015
- 2015-03-02 CN CN201510091939.8A patent/CN104726701B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3361557A (en) * | 1965-03-22 | 1968-01-02 | R N Corp | Processes for direct reduction of ironbearing ores, slags and the like |
| CN101323909A (en) * | 2008-07-17 | 2008-12-17 | 东北大学 | Method of microwave selective reduction roasting-dilute acid leaching nickel oxide ore |
| CN101392320A (en) * | 2008-10-31 | 2009-03-25 | 东北大学 | Method for treating nickel-containing laterite by microwave reducing roasting-goethite precipitation conversion method |
| CN101509069A (en) * | 2009-03-30 | 2009-08-19 | 南通新玮镍钴科技发展有限公司 | Method for selective solvent extraction of heterogenite with full-wet-process |
| CN101629247A (en) * | 2009-07-31 | 2010-01-20 | 南通新玮镍钴科技发展有限公司 | Combined leaching process of white alloy and heterogenite |
| CN101994003A (en) * | 2010-12-10 | 2011-03-30 | 中南大学 | Process for selectively extracting copper and cobalt from heterogenite |
| WO2014000023A1 (en) * | 2012-06-29 | 2014-01-03 | Metaleach Limited | Method for recovering cobalt from cobalt-containing ores |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107779594A (en) * | 2017-08-31 | 2018-03-09 | 广东佳纳能源科技有限公司 | A kind of technique for being segmented reducing leaching Africa heterogenite |
| CN108048671A (en) * | 2017-11-24 | 2018-05-18 | 广东佳纳能源科技有限公司 | A kind of heterogenite leaching method of low cost |
| CN109338122A (en) * | 2018-11-06 | 2019-02-15 | 广东佳纳能源科技有限公司 | A kind of leaching method of heterogenite |
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Effective date of registration: 20180206 Address after: 510651 Changxin Road, Guangzhou, Guangdong, No. 363, No. Patentee after: GUANGDONG INSTITUTE OF RARE METALS Address before: 510651 Changxin Road, Guangzhou, Guangdong, No. 363, No. Patentee before: GUANGDONG RESEARCH INSTITUTE OF INDUSTRIAL TECHNOLOGY (GUANGZHOU RESEARCH INSTITUTE OF NON-FERROUS METALS) |
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Address after: 510651 No. 363, Changxin Road, Guangzhou, Guangdong, Tianhe District Patentee after: Institute of rare metals, Guangdong Academy of Sciences Address before: 510651 No. 363, Changxin Road, Guangzhou, Guangdong, Tianhe District Patentee before: GUANGDONG INSTITUTE OF RARE METALS |