CN101497943B - Method for processing cobalt waste slag and recycling cobalt by sodium persulfate oxidation treatment - Google Patents
Method for processing cobalt waste slag and recycling cobalt by sodium persulfate oxidation treatment Download PDFInfo
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- CN101497943B CN101497943B CN200910058589XA CN200910058589A CN101497943B CN 101497943 B CN101497943 B CN 101497943B CN 200910058589X A CN200910058589X A CN 200910058589XA CN 200910058589 A CN200910058589 A CN 200910058589A CN 101497943 B CN101497943 B CN 101497943B
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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
- Y02P10/20—Recycling
Abstract
The invention discloses a cobalt recovery method by the oxidation treatment of cobalt residues with sodium persulfate, which comprises the following main steps of first-stage leaching, cadmium replacing, filtering and drying, second-stage leaching, filtering, iron removing, cobalt oxidizing and precipitating with sodium persulfate, filtering and cobalt concentrate obtaining. Compared with the similar method, the sodium persulfate oxidation method is used to treat the cobalt residues, so that the content of the cobalt in the enriched cobalt concentrate can reach more than 18.6 percent and is more than 40 times that of the raw materials. Moreover, the invention uses the sodium persulfate oxidation method to enrich and extract the cobalt in the cobalt concentrate, so that the production technology can be obviously simplified and the production cost can be reduced.
Description
Technical field
The present invention relates to the cobalt waste residue recovery technology field of zinc hydrometallurgy, especially a kind of method with processing cobalt waste slag and recycling cobalt by sodium persulfate oxidation treatment.
Background technology
The cobalt waste residue is that zinc hydrometallurgy purifies one of slag, wherein contains the valuable metal cobalt, nickel of recyclable utilization etc.Cobalt metal in the slag is comparatively difficult with respect to cadmium, nickel etc. reclaim.The method that reclaims cobalt at present mainly contains xanthate except that cobalt method, naphthols and Sodium Nitrite remove the cobalt method, the Sodium Borohydride reduction purifies the cobalt method of removing, zinc dust precipitation except that cobalt method (the arsenic salt method of purification, the antimonic salt method of purification, the alloy zinc powder method of purification), the hydrogen peroxide oxidation precipitator method etc.
Hydrogen peroxide precipitator method concrete steps wherein comprise:
1, gets a certain amount of cobalt waste residue, at 600～750 ℃ of following roasting 5～4.5h;
2, cooling adds water and sizes mixing, and adds the vitriol oil then, is warming up to 95 ℃, keeps 4h; Filter then, filtrate contains cobalt and gives over to processing;
3, filter residue adds water again and sizes mixing, and adds the vitriol oil again, and then divides and add concentrated nitric acid, concentrated hydrochloric acid for several times, is warming up to 95 ℃, and the time is kept 3h; Cooling, filtration, twice filtrate merges, and gives over to cobalt liquid and handles;
4, filtrate is concentrated, add sodium carbonate solution and regulate pH value to 3～4, under heated and stirred, slowly add concentration and be 10% sodium sulfide solution,, make and all be converted into the cobaltous sulfide black precipitate to the red disappearance of filtrate;
5, filter, use the clear water washing precipitation, add water, the vitriol oil again, logical pressurized air also is heated to 40～50 ℃, and the oxidation of sulfureted cobalt becomes rose vitriol;
6, filtrate is heated to 70～80 ℃, slowly adds the chlorine bleach liquor, regulating the pH value with 20% sodium carbonate solution is 5～6, is light green until supernatant liquor, and heavy cobalt finishes;
7, filter, filter residue is a cobaltous hydroxide, with the sulphuric acid soln washing, adds diluted hydrochloric acid dissolution again, and the pH value of control terminal point is 4, adds a small amount of superoxol then, makes divalence Fe wherein be oxidized to trivalent Fe, and hydrolytic precipitation gets off;
8, filter, filtrate concentrates, crystallisation by cooling, at 95～105 ℃ of dry cobalt salts that get.
Above-mentioned hydrogen peroxide precipitator method technology controlling and process is comparatively complicated, and production cost is higher, and the cobalt extraction yield is lower, and the content of cobalt is about about 12% in the cobalt salt that obtains.
Summary of the invention
The method that the purpose of this invention is to provide a kind of processing cobalt waste slag and recycling cobalt by sodium persulfate oxidation treatment, adopt the enrichment from the cobalt waste residue of Sodium Persulfate oxidation style to extract cobalt, change traditional technology method, simplify production technique, reduce production costs, and make that cobalt contents is improved in the cobalt concentrate that enrichment obtains.
In order to realize the foregoing invention purpose, the technical solution used in the present invention is as follows:
The method of processing cobalt waste slag and recycling cobalt by sodium persulfate oxidation treatment leaches (one section leach out cobalt and remove cadmium, two sections leachings after deironing) with the cobalt waste residue through two sections adverse currents, uses Sodium Persulfate oxidation precipitation cobalt again, reaches the purpose of enriched in cobalt.
Key step comprises:
(1), one section leaching:
Purifying slag (be the cobalt waste residue, or claim fresh cobalt slag) with the fresh cobalt of zinc hydrometallurgy is raw material, adds water to make slurry, pumps in one section leaching vat, adds the vitriol oil, keeps PH=2.0～3.0, carries out one section leaching, and extraction time 2～3 hours gets one section leach liquor.
(2), displacement cadmium:
One section leach liquor of above-mentioned steps (1) is filtered, and filtrate pumps in the cadmium displacement slot, displaces Spongy Cadmium (extracting Spongy Cadmium etc. as adopting zinc dust precipitation) by cadmium replacing process commonly used, pulls Spongy Cadmium out, obtains displacement liquid.
(3), filtration and dry:
The displacement liquid of above-mentioned steps (2) is filtered, contain the cobalt that leached etc. in the filtrate, filtrate for later use; Contain cobalt and other metallic cations of also not leaching in the filter residue,, get dried filter residue the gained filter residue and drying, standby.
(4), two sections leachings:
With the method slurrying in (1) more set by step of the dried filter residue of above-mentioned steps (3), add the vitriol oil again, two sections leachings are carried out in PH=1.5～2.5, about 1～2 hour of extraction time, two sections leach liquors.
(5), filter:
Two sections leach liquors of above-mentioned steps (4) are filtered, and cobalt mainly enters filtrate, gets filtrate for later use.
(6), deironing:
The filtrate of above-mentioned steps (3) and the filtrate of step (5) are merged, carry out deironing and handle (can adopt yellow phosphate ferrovanadium process etc.), filter then, iron is removed with filter residue, obtains filtrate.
(7), Sodium Persulfate oxidation precipitation cobalt:
The filtrate of above-mentioned steps (6) is warmed up to about 70～90 ℃, every 20～40 minutes, divide 4～5 times and add the solid Sodium Persulfate, reach excessive 7～9 times (along with the increase of Sodium Persulfate consumption, Fe, Mn, Co, Ni is all oxidized, reach purpose with the cobalt complete oxidation, according to experimental result, adopt excessive 7～9 times add-on comparatively suitable, be 7～9 times of the molar weight that contains cobalt in the filtrate), reacted 1.5～3 hours, use sodium hydroxide solution, PH is between 5.0～5.2 in control, makes the divalence cobalt oxidation become the trivalent cobalt, so that cobalt is precipitated, get reacted mixed solution from solution.
(8) filter, get cobalt concentrate:
The reacted mixed solution of above-mentioned steps (7) is filtered, and the throw out that obtains is cobalt concentrate.
Compared with prior art, the invention has the beneficial effects as follows:
Through and with class methods relatively, adopt Sodium Persulfate oxidative treatment cobalt waste residue of the present invention, the content of cobalt can reach more than 18.6% in the cobalt concentrate of enrichment, be in the raw material more than 40 times.
And, adopt Sodium Persulfate oxidation style of the present invention enrichment from the cobalt waste residue to extract cobalt, also can obviously simplify production technique, reduce production costs.
Embodiment
The present invention is described in further detail below in conjunction with embodiment.
But this should be interpreted as that the scope of the above-mentioned theme of the present invention only limits to following embodiment.
Embodiment 1
The method key step of present embodiment processing cobalt waste slag and recycling cobalt by sodium persulfate oxidation treatment comprises:
(1), one section leaching:
With the fresh cobalt purification slag of zinc hydrometallurgy is raw material (add-on gets final product with reactive tank energy slurrying and stirring), adds water and makes slurry, pumps in one section leaching vat, adds the vitriol oil, and PH=2.0 carries out one section leaching, and extraction time 2 hours gets one section leach liquor.
(2), displacement cadmium:
One section leach liquor of above-mentioned steps (1) is filtered, and filtrate pumps in the cadmium displacement slot, and the cadmium replacing process by commonly used goes out Spongy Cadmium with zinc dust precipitation, obtains displacement liquid.
(3), filtration and dry:
The displacement liquid of above-mentioned steps (2) is filtered, contain the cobalt that leached etc. in the filtrate, filtrate for later use; Contain cobalt and other metallic cations of also not leaching in the filter residue,, get dried filter residue the gained filter residue and drying, standby.
(4), two sections leachings:
With the method slurrying in (1) more set by step of the dried filter residue of above-mentioned steps (3), add the vitriol oil again, PH=1.5 carries out two sections leachings, about 1.5 hours of extraction time, two sections leach liquors.
(5), filter:
Two sections leach liquors of above-mentioned steps (4) are filtered, and cobalt mainly enters filtrate, gets filtrate for later use.
(6), deironing:
The filtrate of above-mentioned steps (3) and the filtrate of step (5) are merged, adopt yellow phosphate ferrovanadium process to carry out deironing and handle, filter then, iron is removed with filter residue, obtains filtrate.
(7), Sodium Persulfate oxidation precipitation cobalt:
The filtrate of above-mentioned steps (6) is warmed up to about about 75 ℃, every 20 minutes, divide 4～5 times and add the solid Sodium Persulfate, total add-on reaches excessive 7 times, reacted 1.5 hours, and regulated PH to 5.0～5.2, make the divalence cobalt oxidation become the trivalent cobalt with sodium hydroxide solution, so that cobalt is precipitated, get reacted mixed solution from solution.
(8) filter, get cobalt concentrate:
The reacted mixed solution of above-mentioned steps (7) is filtered, and the throw out that obtains is cobalt concentrate.
Embodiment 2
The method key step of present embodiment processing cobalt waste slag and recycling cobalt by sodium persulfate oxidation treatment comprises:
(1), one section leaching:
Purifying slag with the fresh cobalt of zinc hydrometallurgy is raw material, adds water and makes slurry, pumps in one section leaching vat, adds the vitriol oil, and PH=2.5 carries out one section leaching, and extraction time 2.5 hours gets one section leach liquor.
(2), displacement cadmium:
One section leach liquor of above-mentioned steps (1) is filtered, and filtrate pumps in the cadmium displacement slot, and the cadmium replacing process by commonly used goes out Spongy Cadmium with zinc dust precipitation, obtains displacement liquid.
(3), filtration and dry:
The displacement liquid of above-mentioned steps (2) is filtered, contain the cobalt that leached etc. in the filtrate, filtrate for later use; Contain cobalt and other metallic cations of also not leaching in the filter residue,, get dried filter residue the gained filter residue and drying, standby.
(4), two sections leachings:
With the method slurrying in (1) more set by step of the dried filter residue of above-mentioned steps (3), add the vitriol oil again, PH=2.0 carries out two sections leachings, about 2 hours of extraction time, two sections leach liquors.
(5), filter:
Two sections leach liquors of above-mentioned steps (4) are filtered, and cobalt mainly enters filtrate, gets filtrate for later use.
(6), deironing:
The filtrate of above-mentioned steps (3) and the filtrate of step (5) are merged, adopt yellow phosphate ferrovanadium process to carry out deironing and handle, filter then, iron is removed with filter residue, obtains filtrate.
(7), Sodium Persulfate oxidation precipitation cobalt:
The filtrate of above-mentioned steps (6) is warmed up to about about 80 ℃, every 30 minutes, divide 4～5 times and add the solid Sodium Persulfate, total add-on reaches excessive 8 times, regulate PH to 5.0～5.2 with sodium hydroxide solution, reacted 2 hours, make the divalence cobalt oxidation become the trivalent cobalt, so that cobalt is precipitated, get reacted mixed solution from solution.
(8) filter, get cobalt concentrate:
The reacted mixed solution of above-mentioned steps (7) is filtered, and the throw out that obtains is cobalt concentrate.
Embodiment 3
The method key step of present embodiment processing cobalt waste slag and recycling cobalt by sodium persulfate oxidation treatment comprises:
(1), one section leaching:
Purifying slag with the fresh cobalt of zinc hydrometallurgy is raw material, adds water and makes slurry, pumps in one section leaching vat, adds the vitriol oil, and PH=3.0 carries out one section leaching, and extraction time 3 hours gets one section leach liquor.
(2), displacement cadmium:
One section leach liquor of above-mentioned steps (1) is filtered, and filtrate pumps in the cadmium displacement slot, and the cadmium replacing process by commonly used goes out Spongy Cadmium with zinc dust precipitation, obtains displacement liquid.
(3), filtration and dry:
The displacement liquid of above-mentioned steps (2) is filtered, contain the cobalt that leached etc. in the filtrate, filtrate for later use; Contain cobalt and other metallic cations of also not leaching in the filter residue,, get dried filter residue the gained filter residue and drying, standby.
(4), two sections leachings:
With the method slurrying in (1) more set by step of the dried filter residue of above-mentioned steps (3), add the vitriol oil again, PH=2.5 carries out two sections leachings, about 3 hours of extraction time, two sections leach liquors.
(5), filter:
Two sections leach liquors of above-mentioned steps (4) are filtered, and cobalt mainly enters filtrate, gets filtrate for later use.
(6), deironing:
The filtrate of above-mentioned steps (3) and the filtrate of step (5) are merged, adopt yellow phosphate ferrovanadium process to carry out deironing and handle, filter then, iron is removed with filter residue, obtains filtrate.
(7), Sodium Persulfate oxidation precipitation cobalt:
The filtrate of above-mentioned steps (6) is warmed up to about about 85 ℃, every 40 minutes, divide 4～5 times and add the solid Sodium Persulfate, total add-on reaches excessive 9 times, regulate PH to 5.0～5.2 with sodium hydroxide solution, reacted 3 hours, make the divalence cobalt oxidation become the trivalent cobalt, so that cobalt is precipitated, get reacted mixed solution from solution.
(8) filter, get cobalt concentrate:
The reacted mixed solution of above-mentioned steps (7) is filtered, and the throw out that obtains is cobalt concentrate.
Claims (3)
1. the method for processing cobalt waste slag and recycling cobalt by sodium persulfate oxidation treatment, key step comprises:
(1), one section leaching:
With the cobalt waste residue is raw material, adds an amount of water, makes slurry, pumps in one section leaching vat, adds the vitriol oil, keeps pH=2.0～3.0, carries out one section leaching, and extraction time 2～3 hours gets one section leach liquor;
(2), displacement cadmium:
One section leach liquor of above-mentioned steps (1) is filtered, and filtrate pumps in the cadmium displacement slot, displaces Spongy Cadmium by cadmium replacing process commonly used, obtains displacement liquid;
(3), filtration and dry:
The displacement liquid of above-mentioned steps (2) is filtered filtrate for later use; With the gained filter residue and drying, get dried filter residue, standby;
(4), two sections leachings:
With the method slurrying in (1) more set by step of the dried filter residue of above-mentioned steps (3), add the vitriol oil again, keep pH=1.5～2.5, carry out two sections leachings, extraction time 1～2 hour, two sections leach liquors;
(5), filter:
Two sections leach liquors of above-mentioned steps (4) are filtered, get filtrate for later use;
(6), deironing:
The filtrate of above-mentioned steps (3) and the filtrate of step (5) are merged, carry out deironing and handle, filter then, obtain filtrate;
(7), Sodium Persulfate oxidation precipitation cobalt:
The filtrate of above-mentioned steps (6) is warmed up to 70～90 ℃, every 20～40 minutes, divides 4～5 times and add the solid Sodium Persulfate, total add-on of Sodium Persulfate reaches excessive 7～9 times; React after 1.5～3 hours, regulating pH with sodium hydroxide solution again is 5.0～5.2; Get reacted mixed solution;
(8) filter, get cobalt concentrate:
The reacted mixed solution of above-mentioned steps (7) is filtered, and the throw out that obtains is cobalt concentrate.
2. method according to claim 1 is characterized in that: described displacement cadmium technology is to adopt zinc dust precipitation to extract Spongy Cadmium.
3. method according to claim 2 is characterized in that: it is to adopt yellow phosphate ferrovanadium process to handle that described deironing is handled.
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Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101974691B (en) * | 2010-11-10 | 2012-10-03 | 白银有色集团股份有限公司 | Method for recovering cobalt in cobalt-containing waste residues from zinc smelting |
| CN103014346A (en) * | 2012-12-03 | 2013-04-03 | 河池市津泰资源再生有限公司 | Process method for separating zinc, iron and cobalt and nickel ore concentrates from cobalt and nickel slag |
| CN104726717B (en) * | 2015-04-01 | 2017-04-19 | 云南驰宏锌锗股份有限公司 | Method for recovering cobalt from inverse antimony purified cobalt residue |
| CN107601582A (en) * | 2017-10-12 | 2018-01-19 | 南通新玮镍钴科技发展有限公司 | A kind of quick method for preparing cobalt oxide |
| CN108203764B (en) * | 2018-01-09 | 2020-03-27 | 云南驰宏资源综合利用有限公司 | Method for producing cobalt concentrate by using microwave-calcined zinc hydrometallurgical purified cobalt-nickel slag |
| CN108227668A (en) * | 2018-04-04 | 2018-06-29 | 上海天坛助剂有限公司 | Sodium peroxydisulfate and potassium peroxydisulfate process units DCS control systems and control method |
| CN110195160A (en) * | 2019-06-10 | 2019-09-03 | 赤峰中色锌业有限公司 | A kind of comprehensive recovering process of clean melt cinder of wet-process zinc metallurgy |
| CN114058872A (en) * | 2021-11-24 | 2022-02-18 | 白银有色集团股份有限公司 | Method for improving grade of cobalt slag of zinc hydrometallurgy |
| CN114854996A (en) * | 2022-05-07 | 2022-08-05 | 金川集团股份有限公司 | Method for removing antimony by persulfate advanced oxidation method |
| CN115011818A (en) * | 2022-06-15 | 2022-09-06 | 上海寰泰绿钒科技有限公司 | Method for extracting vanadium from stone coal |
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