CN113005303A - Method for extracting cobalt from cadmium-poor high-cobalt liquid - Google Patents
Method for extracting cobalt from cadmium-poor high-cobalt liquid Download PDFInfo
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- CN113005303A CN113005303A CN202110323955.0A CN202110323955A CN113005303A CN 113005303 A CN113005303 A CN 113005303A CN 202110323955 A CN202110323955 A CN 202110323955A CN 113005303 A CN113005303 A CN 113005303A
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- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 211
- 239000010941 cobalt Substances 0.000 title claims abstract description 211
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 158
- 239000007788 liquid Substances 0.000 title claims abstract description 75
- 238000000034 method Methods 0.000 title claims abstract description 51
- 239000002893 slag Substances 0.000 claims abstract description 141
- 229910052793 cadmium Inorganic materials 0.000 claims abstract description 90
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 61
- 239000012629 purifying agent Substances 0.000 claims abstract description 49
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 44
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229910001429 cobalt ion Inorganic materials 0.000 claims abstract description 34
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000002244 precipitate Substances 0.000 claims abstract description 32
- 239000002699 waste material Substances 0.000 claims abstract description 32
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 27
- 230000003213 activating effect Effects 0.000 claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- 238000001914 filtration Methods 0.000 claims abstract description 20
- 239000003792 electrolyte Substances 0.000 claims abstract description 19
- 239000011787 zinc oxide Substances 0.000 claims abstract description 18
- 238000002156 mixing Methods 0.000 claims abstract description 13
- 238000005406 washing Methods 0.000 claims abstract description 12
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 61
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 50
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 43
- 229910052725 zinc Inorganic materials 0.000 claims description 34
- 239000011701 zinc Substances 0.000 claims description 34
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 claims description 29
- 229910052742 iron Inorganic materials 0.000 claims description 25
- 238000003825 pressing Methods 0.000 claims description 23
- 238000005554 pickling Methods 0.000 claims description 21
- 239000002253 acid Substances 0.000 claims description 15
- 239000000843 powder Substances 0.000 claims description 11
- 238000005868 electrolysis reaction Methods 0.000 claims description 10
- 238000004537 pulping Methods 0.000 claims description 8
- 230000001376 precipitating effect Effects 0.000 claims description 7
- 241000276489 Merlangius merlangus Species 0.000 claims description 4
- 239000008394 flocculating agent Substances 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 238000000605 extraction Methods 0.000 abstract description 9
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- 150000002739 metals Chemical class 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 2
- 238000005086 pumping Methods 0.000 description 20
- 238000002386 leaching Methods 0.000 description 19
- 239000013522 chelant Substances 0.000 description 15
- 230000007935 neutral effect Effects 0.000 description 14
- 238000011085 pressure filtration Methods 0.000 description 12
- 230000003647 oxidation Effects 0.000 description 8
- 238000007254 oxidation reaction Methods 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 6
- 238000005352 clarification Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 230000008901 benefit Effects 0.000 description 5
- 238000006386 neutralization reaction Methods 0.000 description 5
- 238000000746 purification Methods 0.000 description 5
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 229910052748 manganese Inorganic materials 0.000 description 4
- 239000011572 manganese Substances 0.000 description 4
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 4
- 239000012286 potassium permanganate Substances 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 238000003723 Smelting Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 229910001437 manganese ion Inorganic materials 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 2
- 238000010668 complexation reaction Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229910018916 CoOOH Inorganic materials 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000009854 hydrometallurgy Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012946 outsourcing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0453—Treatment or purification of solutions, e.g. obtained by leaching
- C22B23/0461—Treatment or purification of solutions, e.g. obtained by leaching by chemical methods
- C22B23/0469—Treatment or purification of solutions, e.g. obtained by leaching by chemical methods by chemical substitution, e.g. by cementation
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/02—Roasting processes
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0453—Treatment or purification of solutions, e.g. obtained by leaching
- C22B23/0461—Treatment or purification of solutions, e.g. obtained by leaching by chemical methods
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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 belongs to the field of cobalt extraction technology application, and particularly relates to a method for extracting cobalt from a cadmium-poor high-cobalt solution, which comprises the following steps: adding zinc powder into the low-cadmium high-cobalt solution, and reacting and filtering to obtain a cadmium-removed solution; adding hydrogen peroxide and zinc oxide into the cadmium-removed solution, reacting and filtering to obtain iron-removed solution; adding a purifying agent and an activating agent into the iron-removed liquid to obtain a cobalt ion precipitate; mixing the cobalt ion precipitate with waste electrolyte for reaction to obtain acid-washed cobalt slag; and washing and baking the acid-washed cobalt slag to obtain the high-cobalt slag dry slag. The invention solves the problem of difficult sale due to low cobalt content, fully utilizes valuable metals, changes waste into valuable materials and realizes circular economy.
Description
Technical Field
The invention belongs to the field of cobalt extraction technology application, and particularly relates to a method for extracting cobalt from a cadmium-poor high-cobalt solution.
Background
The zinc smelting mode is mainly zinc smelting by a wet method at present, and dangerous waste solid slag which is rich in valuable metals such as copper, cadmium, cobalt, nickel and the like can be generated in the production process due to the fact that raw materials are rich in copper, cadmium, nickel and cobalt in the production process, and the dangerous waste solid slag is removed by adding zinc powder in the purification process, so that slag is generated. Wherein the nickel-cobalt slag is mainly produced by the second-stage purification of the purification process, part of production enterprises directly sell or pile the nickel-cobalt slag at low price, and part of enterprises enrich the nickel-cobalt slag into high-cobalt slag for sale or pile. At present, the problems of low cobalt market price, low cobalt slag grade, high downstream unit processing cost and the like cause difficult outsourcing and great economic benefit loss; if stockpiled, the method causes capital and site occupation, and has certain environmental protection problems. Therefore, the extraction and recovery of the zinc are not only urgent needs in the aspect of environmental protection, but also are a benefit increasing point of the zinc smelting process. At present, individual enterprises mainly adopt an oxidation cobalt precipitation method for recovering cobalt.
Due to the existence of cobalt in the raw material, the nickel-cobalt slag produced by purification in the zinc production process is difficult to sell due to low cobalt content, high zinc content, high water content and small amount of cadmium, and the cobalt content is low after the zinc is recovered by acid washing.
In order to solve the problems, the invention provides a method for extracting cobalt from a cadmium-poor high-cobalt solution.
Disclosure of Invention
An object of the present invention is to solve at least one of the above problems or disadvantages and to provide at least one advantage which will be described later.
The invention also aims to provide a method for extracting cobalt from the low-cadmium high-cobalt solution, which solves the problem of difficult sale due to low cobalt content, fully utilizes valuable metals, changes waste into valuable materials and realizes circular economy.
To achieve these objects and other advantages in accordance with the present invention, there is provided a method for extracting cobalt from a cadmium-depleted high cobalt solution, comprising the steps of:
adding zinc powder into the poor-cadmium high-cobalt solution, reacting and filtering to obtain cadmium slag and cadmium-removed solution;
adding hydrogen peroxide and zinc oxide into the cadmium-removed solution, reacting and filtering to obtain iron-removed solution;
adding a purifying agent and an activating agent into the iron-removed liquid to obtain a cobalt ion precipitate;
mixing the cobalt ion precipitate with waste electrolyte for reaction to obtain acid-washed cobalt slag;
and washing and baking the acid-washed cobalt slag to obtain the high-cobalt slag dry slag.
Preferably, the adding zinc powder into the low-cadmium high-cobalt solution, and after reaction and filtration, obtaining cadmium slag and cadmium-removed solution specifically comprises:
adding zinc powder into the cadmium-poor high cobalt solution at the temperature of 45-60 ℃, reacting for 0.7-1.0h, and performing filter pressing to obtain cadmium slag and cadmium-removed solution;
wherein the weight ratio of the zinc powder to the cadmium in the cadmium-poor cobalt-rich liquid is 2-4: 1.
Preferably, the step of adding hydrogen peroxide and zinc oxide into the solution after cadmium removal, and filtering the solution after reaction to obtain the solution after iron removal specifically comprises the following steps:
adding hydrogen peroxide and zinc oxide into the cadmium-removed solution at the temperature of 60-70 ℃, reacting for 1.0-1.5h, adjusting the pH to 2.5, adding whiting powder, and adjusting the pH to 2.7-3.7;
and adding a flocculating agent, and performing solid-liquid separation to obtain iron-removed liquid and iron slag.
Preferably, the weight ratio of the hydrogen peroxide to the iron is 1.5-2.0:1, and the initial adding weight of the whiting powder is 0.5 times of the weight of the hydrogen peroxide.
Preferably, the step of adding a purifying agent and an activating agent into the iron-removed solution to obtain the cobalt ion precipitate specifically comprises the following steps:
adding 3R-NS purifying agent at 70-80 deg.CReacting with a reagent for 1.0-2.0h to obtain cobalt ion precipitate Co (R-NS)2)3。
Preferably, the weight ratio of the purifying agent to the cobalt in the liquid after iron removal is 20:1, and the weight ratio of the activating agent to the purifying agent is 0.1: 1.
Preferably, the step of mixing the cobalt ion precipitate with the waste electrolyte for reaction to obtain the acid-washed cobalt slag specifically comprises:
precipitating the cobalt ion into Co (R-NS)2)3Mixing with water, adding waste electrolyte, and pickling at 60-70 deg.C for 1.5-2.0 hr to obtain pickling solution;
and adjusting the pH value of the pickling solution to 0.5-1.0, and performing filter pressing to obtain pickled cobalt slag and a zinc-containing solution.
Preferably, the cobalt ion precipitate Co (R-NS)2)3The weight ratio of the waste electrolyte to water is 3-5:1, and the waste electrolyte contains 140-160g/L of acid.
Preferably, the washing and baking of the acid-washed cobalt slag to obtain the high cobalt slag dry slag specifically comprises:
when acid-washed cobalt slag is obtained through filter pressing, clear water at the temperature of 70-75 ℃ is directly added to the acid-washed cobalt slag to wash the acid-washed cobalt slag on a filter press for 2-3 times, and the acid-washed cobalt slag is obtained through filter pressing;
and baking the washed cobalt slag in a baking furnace to obtain the high-cobalt slag dry slag.
Preferably, the method comprises the following steps of adding zinc powder into the low-cadmium high-cobalt solution, reacting and filtering to obtain cadmium slag and cadmium-removed solution:
pulping nickel-cobalt slag and water, adding zinc electrolysis waste liquid, reacting for 2-3h at 75-80 ℃, adjusting the pH value to 5.0, and filtering to obtain the cadmium-poor high-cobalt liquid.
Wherein the volume ratio of the nickel-cobalt slag to the water is 3-5:1, and the zinc electrolyte contains 140-160g/L of acid.
The invention has the advantages of
1. The method for extracting cobalt from the low-cadmium high-cobalt liquid realizes the recovery of cadmium in the purified nickel-cobalt slag, and compared with the prior art, the method for extracting cobalt from the low-cadmium high-cobalt liquid recovers more cadmium in the purified nickel-cobalt slag.
2. The method for extracting cobalt from the low-cadmium high-cobalt solution provided by the invention adopts a novel purifying agent to complex cobalt, does not make requirements on manganese ions in the solution, and is simple and feasible.
3. According to the method for extracting cobalt from the low-cadmium high-cobalt solution, the zinc oxide neutralizer is adopted, so that the neutralizer cost is saved, and the resource is saved.
4. According to the method for extracting cobalt from the low-cadmium high-cobalt solution, the transportation cost is saved after the cobalt is dried by the baking furnace, the drying is not carried out in the prior art, and the external transportation cost is high.
Drawings
Fig. 1 is a schematic flow diagram of a method for extracting cobalt from a cadmium-depleted cobalt-rich liquid according to the invention.
Detailed Description
The present invention is further described in detail below with reference to the attached drawings so that those skilled in the art can implement the invention by referring to the description text.
It will be understood that terms such as "having," "including," and "comprising," as used herein, do not preclude the presence or addition of one or more other elements or groups thereof.
The invention recovers zinc, copper and cadmium from the second clean slag produced in the purification process of the zinc hydrometallurgy, and then obtains the cobalt-poor high cobalt solution with high cobalt taste after treatment.
After the second-stage leaching of the second-stage purifying nickel-cobalt slag, great amount of Zn, Co and Cd are leached into the neutral leaching liquid, so that the present invention extracts Co from the neutral leaching liquid, i.e. from the liquid with low Cd and high Co content.
As shown in fig. 1, the present invention provides a method for extracting cobalt from a cadmium-depleted high cobalt solution, comprising the following steps:
firstly, pulping nickel-cobalt slag and water, then pumping the pulped nickel-cobalt slag and water into a neutral leaching tank, controlling the volume ratio of the nickel-cobalt slag to the water in the tank to be 3-5:1, adding zinc electrolysis waste liquid (containing 140 acids and 160g/L), reacting for 2-3h at the temperature of 75-80 ℃, adjusting the pH value to be 5.0 at the end of the reaction, and filtering to obtain cadmium-depleted high-cobalt liquid and neutral leaching slag;
step two, pumping the low-cadmium high-cobalt solution into a cadmium removal tank, adding zinc powder to replace cadmium at the temperature of 45-60 ℃, wherein the weight ratio of the zinc powder to the cadmium in the low-cadmium high-cobalt solution is 2-4:1 (the cadmium content is not greatly fluctuated under the normal condition, and the adding amount of the zinc powder is 1.0-1.5kg/m according to the volume amount3) After reacting for 0.7-1.0h, performing filter pressing to obtain cadmium slag and cadmium-removed liquid;
thirdly, throwing the cadmium-removed liquid into an iron removing tank, adding hydrogen peroxide at the temperature of 60-70 ℃, reacting for 1.0-1.5h, neutralizing, adding white powder when adjusting the pH to 2.5, wherein the initial addition amount is 0.5 times of the amount of hydrogen peroxide, continuously adjusting the pH to 2.7-3.7 to achieve the hydrolysis condition of trivalent iron, adding a small amount of flocculant for clarification, and performing filter pressing to obtain iron-removed liquid and iron slag; the principle of the step is that after ferrous iron is oxidized into ferric iron, the ferric iron is hydrolyzed to generate acid, and the pH value is adjusted by increasing the white powder to ensure that the hydrolysis reaction is thorough.
Step four, the iron-removed liquid is pumped into a cobalt extraction reaction tank, a purifying agent 3R-NS and an activating agent are added under the condition of 70-80 ℃, and the reaction is carried out for 1.0-2.0h to obtain cobalt ion precipitate Co (R-NS)2)3；
The weight ratio of the purifying agent to the cobalt in the iron-removed liquid is 20:1, the weight ratio of the activating agent to the purifying agent is 0.1:1, the activating agent has a catalytic effect on the purifying agent, and the novel purifying agent forms chelate precipitates from cobalt ions in the solution;
step five, precipitating the cobalt ion precipitate Co (R-NS)2)3Putting the mixture into a pickling tank, mixing the chelate with water at a ratio of 3-5:1, adding waste electrolyte (containing 140-;
step six, when the acid-washed cobalt slag is obtained through pressure filtration in the step five, clear water at the temperature of 70-75 ℃ is directly added to wash the acid-washed cobalt slag on a pressure filter, the washing is carried out for 2-3 times, and the pressure filtration is carried out, so that the water-washed cobalt slag is obtained; and baking the washed cobalt slag in a baking furnace to obtain high-cobalt slag dry slag, wherein the cobalt content is increased to about 15 percent, which is increased by about 4-5 times compared with the original cobalt content.
The following examples are provided to illustrate the technical problems solved and technical effects achieved by the present invention.
Example 1
The invention provides a method for extracting cobalt from a low-cadmium high-cobalt solution, which comprises the following steps:
firstly, pulping nickel-cobalt slag and water, then pumping the pulped nickel-cobalt slag and water into a neutral leaching tank, controlling the volume ratio of the nickel-cobalt slag to the water in the tank to be 4:1, adding zinc electrolysis waste liquid (containing 160g/L of acid), reacting for 3 hours at the temperature of 80 ℃, controlling the pH value to be 2.5 in the process, adjusting the pH value to be 5.0 at the end point of the reaction, and filtering to obtain a cadmium-depleted high-cobalt liquid and neutral leaching slag;
step two, pumping the low-cadmium high-cobalt solution into a cadmium removal tank, adding zinc powder to replace cadmium at the temperature of 50 ℃, reacting for 0.7h, and performing filter pressing to obtain cadmium slag and cadmium removal solution, wherein the weight ratio of the zinc powder to the cadmium in the low-cadmium high-cobalt solution is 3: 1;
thirdly, putting the cadmium-removed liquid into an iron removing tank, adding hydrogen peroxide at the temperature of 60 ℃, wherein the weight ratio of the hydrogen peroxide to the iron is 2:1, measuring the pH value in time after the reaction starts, adding zinc oxide for neutralization according to the pH condition, adjusting the pH value to 3.5 in the process, adding white powder for slagging after reacting for 40 minutes, continuously adjusting the end point pH value to 5.0, adding a small amount of flocculant for clarification, and performing filter pressing to obtain iron-removed liquid and iron slag;
step four, pumping the iron-removed liquid into a cobalt extraction reaction tank, adding a purifying agent 3R-NS and an activating agent at the temperature of 75 ℃, and reacting for 1.5 hours to obtain a cobalt ion precipitate Co (R-NS)2)3；
The weight ratio of the purifying agent to the cobalt in the iron-removed liquid is 20:1, the weight ratio of the activating agent to the purifying agent is 0.1:1, the activating agent has a catalytic effect on the purifying agent, and the novel purifying agent forms chelate precipitates from cobalt ions in the solution;
step five, the stepThe cobalt ion precipitate Co (R-NS)2)3Putting the mixture into a pickling tank, mixing the chelate with water at a ratio of 3:1, adding waste electrolyte (containing 160g/L acid), pickling for 1.5h at 65 ℃ to obtain pickling solution, adjusting the pH of the pickling solution to 0.5, leaching and recovering zinc in the chelate, reducing the zinc content of cobalt slag, and performing filter pressing to obtain pickled cobalt slag and a zinc-containing solution;
step six, when the acid-washed cobalt slag is obtained through pressure filtration in the step five, clear water at 70 ℃ is directly added to wash the acid-washed cobalt slag on a pressure filter, the washing is carried out for 2 times, and the pressure filtration is carried out to obtain the washed cobalt slag; and baking the washed cobalt slag in a baking furnace to obtain high-cobalt slag dry slag with the cobalt content of 15%.
Example 2
The invention provides a method for extracting cobalt from a low-cadmium high-cobalt solution, which comprises the following steps:
firstly, pulping nickel-cobalt slag and water, then pumping the pulped nickel-cobalt slag and water into a neutral leaching tank, controlling the volume ratio of the nickel-cobalt slag to the water in the tank to be 3:1, adding zinc electrolysis waste liquid (containing 160g/L of acid), reacting for 3 hours at the temperature of 80 ℃, adjusting the pH value to be 5.0 at the end point of the reaction, and filtering to obtain a cadmium-poor high-cobalt liquid and neutral leaching slag;
step two, pumping the low-cadmium high-cobalt solution into a cadmium removal tank, adding zinc powder to replace cadmium at the temperature of 55 ℃, reacting for 0.7h, and performing filter pressing to obtain cadmium slag and cadmium removal solution, wherein the weight ratio of the zinc powder to the cadmium in the low-cadmium high-cobalt solution is 2: 1;
thirdly, putting the cadmium-removed liquid into an iron removing tank, adding hydrogen peroxide and zinc oxide at the temperature of 65 ℃, wherein the weight ratio of the hydrogen peroxide to the iron is 1.6:1, measuring the pH value in time after the reaction starts, adding the zinc oxide for neutralization according to the pH condition, adjusting the pH value to 3.5 in the process, adding white powder for slagging after reacting for 40 minutes, continuously adjusting the end point pH to 5.0, adding a small amount of flocculant for clarification, and performing filter pressing to obtain the iron-removed liquid and iron slag;
step four, pumping the iron-removed liquid into a cobalt extraction reaction tank, adding a purifying agent 3R-NS and an activating agent at the temperature of 70 ℃, and reacting for 1.0 hour to obtain a cobalt ion precipitate Co (R-NS)2)3；
The weight ratio of the purifying agent to the cobalt in the iron-removed liquid is 20:1, the weight ratio of the activating agent to the purifying agent is 0.1:1, the activating agent has a catalytic effect on the purifying agent, and the novel purifying agent forms chelate precipitates from cobalt ions in the solution;
step five, precipitating the cobalt ion precipitate Co (R-NS)2)3Putting the mixture into a pickling tank, mixing the chelate with water at a ratio of 4:1, adding waste electrolyte (containing 160g/L acid), pickling for 1.5h at 65 ℃ to obtain pickling solution, adjusting the pH of the pickling solution to 0.7, leaching and recovering zinc in the chelate, reducing the zinc content of cobalt slag, and performing filter pressing to obtain pickled cobalt slag and a zinc-containing solution;
step six, when the acid-washed cobalt slag is obtained through pressure filtration in the step five, clear water with the temperature of 75 ℃ is directly added to wash the acid-washed cobalt slag on a pressure filter, the washing is carried out for 2 to 3 times, and the pressure filtration is carried out, so that the water-washed cobalt slag is obtained; and baking the washed cobalt slag in a baking furnace to obtain high-cobalt slag dry slag with the cobalt content of 14%.
Example 3
The invention provides a method for extracting cobalt from a low-cadmium high-cobalt solution, which comprises the following steps:
firstly, pulping nickel-cobalt slag and water, then pumping the pulped nickel-cobalt slag and water into a neutral leaching tank, controlling the volume ratio of the nickel-cobalt slag to the water in the tank to be 5:1, adding zinc electrolysis waste liquid (containing 160g/L of acid), reacting for 3.0h at the temperature of 80 ℃, adjusting the pH value to be 5.0 at the end point of the reaction, and filtering to obtain a cadmium-poor high-cobalt solution and neutral leaching slag;
step two, pumping the low-cadmium high-cobalt solution into a cadmium removal tank, adding zinc powder to replace cadmium at 55 ℃, wherein the weight ratio of the zinc powder to the cadmium in the low-cadmium high-cobalt solution is 4:1 (the cadmium content is not greatly fluctuated under normal conditions, and the adding amount of the zinc powder is 1.0-1.5kg/m according to the volume amount3) After reacting for 0.8h, performing filter pressing to obtain cadmium slag and cadmium-removed liquid;
thirdly, pumping the cadmium-removed liquid into an iron removing tank, adding hydrogen peroxide and zinc oxide at the temperature of 60 ℃, wherein the weight ratio of the hydrogen peroxide to the iron is 1.8:1, measuring the pH value in time after the reaction starts, adding the zinc oxide for neutralization according to the pH condition, adjusting the pH value to 3.5 in the process, adding white powder for slagging after reacting for 40 minutes, continuously adjusting the end point pH to 5.0, adding a small amount of flocculant for clarification, and performing filter pressing to obtain the iron-removed liquid and iron slag;
step four, pumping the iron-removed liquid into a cobalt extraction reaction tank, adding a purifying agent 3R-NS and an activating agent at 78 ℃, and reacting for 2 hours to obtain a cobalt ion precipitate Co (R-NS)2)3；
The weight ratio of the purifying agent to the cobalt in the iron-removed liquid is 20:1, the weight ratio of the activating agent to the purifying agent is 0.1:1, the activating agent has a catalytic effect on the purifying agent, and the novel purifying agent forms chelate precipitates from cobalt ions in the solution;
step five, precipitating the cobalt ion precipitate Co (R-NS)2)3Putting the mixture into a pickling tank, mixing the chelate with water at a ratio of 5:1, adding waste electrolyte (containing 150g/L acid), pickling for 1.5h at 70 ℃ to obtain pickling solution, adjusting the pH of the pickling solution to 0.5, leaching and recovering zinc in the chelate, reducing the zinc content of cobalt slag, and performing filter pressing to obtain pickled cobalt slag and a zinc-containing solution;
step six, when the acid-washed cobalt slag is obtained through pressure filtration in the step five, clear water at 70 ℃ is directly added to wash the acid-washed cobalt slag on a pressure filter, the washing is carried out for 2 to 3 times, and the pressure filtration is carried out to obtain the washed cobalt slag; and baking the washed cobalt slag in a baking furnace to obtain high-cobalt slag dry slag with the cobalt content of 18%.
Example 4
The invention provides a method for extracting cobalt from a low-cadmium high-cobalt solution, which comprises the following steps:
firstly, pulping nickel-cobalt slag and water, then pumping the pulped nickel-cobalt slag and water into a neutral leaching tank, controlling the volume ratio of the nickel-cobalt slag to the water in the tank to be 4.5:1, adding zinc electrolysis waste liquid (containing 160g/L of acid), reacting for 3.0h at the temperature of 80 ℃, adjusting the pH value to be 5.0 at the end point of the reaction, and filtering to obtain a cadmium-poor high-cobalt solution and neutral leaching slag;
step two, pumping the low-cadmium high-cobalt solution into a cadmium removal tank, adding zinc powder to replace cadmium at the temperature of 60 ℃, wherein the weight ratio of the zinc powder to the cadmium in the low-cadmium high-cobalt solution is 3.5:1 (the cadmium content is not greatly fluctuated under the normal condition, and the zinc powder is addedThe amount is 1.0-1.5kg/m by volume3) After reacting for 0.7h, performing filter pressing to obtain cadmium slag and cadmium-removed liquid;
thirdly, pumping the cadmium-removed liquid into an iron removing tank, adding hydrogen peroxide and zinc oxide at the temperature of 60 ℃, wherein the weight ratio of the hydrogen peroxide to the iron is 2.0:1, measuring the pH value in time after the reaction starts, adding the zinc oxide for neutralization according to the pH condition, adjusting the pH value to 3.5 in the process, adding white powder for slagging after reacting for 40 minutes, continuously adjusting the end point pH to 5.0, adding a small amount of flocculant for clarification, and performing filter pressing to obtain the iron-removed liquid and iron slag;
step four, pumping the iron-removed liquid into a cobalt extraction reaction tank, adding a purifying agent 3R-NS and an activating agent at the temperature of 75 ℃, and reacting for 1.8 hours to obtain a cobalt ion precipitate Co (R-NS)2)3；
The weight ratio of the purifying agent to the cobalt in the iron-removed liquid is 20:1, the weight ratio of the activating agent to the purifying agent is 0.1:1, the activating agent has a catalytic effect on the purifying agent, and the novel purifying agent forms chelate precipitates from cobalt ions in the solution;
step five, precipitating the cobalt ion precipitate Co (R-NS)2)3Putting the mixture into a pickling tank, wherein the mixing ratio of the chelate to water is 3:1, adding waste electrolyte (containing 140-;
step six, when the acid-washed cobalt slag is obtained through pressure filtration in the step five, clear water at 70 ℃ is directly added to wash the acid-washed cobalt slag on a pressure filter, the washing is carried out for 2 to 3 times, and the pressure filtration is carried out to obtain the washed cobalt slag; and baking the washed cobalt slag in a baking furnace to obtain high-cobalt slag dry slag with the cobalt content of 17%.
Example 5
The invention provides a method for extracting cobalt from a low-cadmium high-cobalt solution, which comprises the following steps:
firstly, pulping nickel-cobalt slag and water, then pumping the pulped nickel-cobalt slag and water into a neutral leaching tank, controlling the weight ratio of the nickel-cobalt slag to the water in the tank to be 5:1, adding zinc electrolysis waste liquid (containing 150g/L of acid), reacting for 3.0h at the temperature of 80 ℃, adjusting the pH value to be 5.0 at the end point of the reaction, and filtering to obtain cadmium-depleted high-cobalt liquid and neutral leaching slag;
step two, pumping the low-cadmium high-cobalt solution into a cadmium removal tank, adding zinc powder to replace cadmium at 50 ℃, reacting for 0.7h after the zinc powder and the cadmium in the low-cadmium high-cobalt solution are in a weight ratio of 3:1 (the cadmium content is not greatly fluctuated under normal conditions, and the adding amount of the zinc powder is 1.0-1.5kg/m3 by volume), and performing filter pressing to obtain cadmium slag and cadmium-removed solution;
thirdly, pumping the cadmium-removed liquid into an iron removing tank, adding hydrogen peroxide and zinc oxide at the temperature of 60 ℃, wherein the weight ratio of the hydrogen peroxide to the iron is 1.8:1, measuring the pH value in time after the reaction starts, adding the zinc oxide for neutralization according to the pH condition, adjusting the pH value to 3.5 in the process, adding white powder for slagging after reacting for 40 minutes, continuously adjusting the end point pH to 5.0, adding a small amount of flocculant for clarification, and performing filter pressing to obtain the iron-removed liquid and iron slag;
step four, pumping the iron-removed liquid into a cobalt extraction reaction tank, adding a purifying agent 3R-NS and an activating agent at the temperature of 75 ℃, and reacting for 1.5 hours to obtain a cobalt ion precipitate Co (R-NS)2)3；
The weight ratio of the purifying agent to the cobalt in the iron-removed liquid is 20:1, the weight ratio of the activating agent to the purifying agent is 0.1:1, the activating agent has a catalytic effect on the purifying agent, and the novel purifying agent forms chelate precipitates from cobalt ions in the solution;
step five, precipitating the cobalt ion precipitate Co (R-NS)2)3Putting the mixture into a pickling tank, wherein the mixing ratio of the chelate to water is 3:1, adding waste electrolyte (containing 140-;
step six, when the acid-washed cobalt slag is obtained through pressure filtration in the step five, clear water at 70 ℃ is directly added to wash the acid-washed cobalt slag on a pressure filter, the washing is carried out for 2 to 3 times, and the pressure filtration is carried out to obtain the washed cobalt slag; and baking the washed cobalt slag in a baking furnace to obtain high-cobalt slag dry slag with the cobalt content of 16%.
In the prior art, the cobalt slag is only subjected to zinc recovery post-treatment, and the cobalt content is only about 2 percent. Some enterprises adopt potassium permanganate to oxidize cobalt, but because the manganese content in the system is high, the cobalt can be oxidized only after the manganese is oxidized, so the potassium permanganate consumes a lot and the cost is high. From the above examples 1-5, it can be seen that the cobalt content finally obtained is above 15%, and for the prior art, the method further enriches and sells the cobalt at a higher price, reduces transportation cost, and has significant beneficial effects.
The invention also provides a comparative experiment of example 1, wherein the leaching, cadmium removal and iron removal processes are the same, namely when cobalt is precipitated (step five), potassium permanganate is added in the comparative experiment, and the purifying agent is added in example 1, and the two processes are Co in solution2+The oxidation is carried out first, with the difference that the complexation method is different. The cobalt enriched by the oxidation method contains 12-17% of cobalt, which is not much different from the cobalt recovered by the purifying agent, but both of the cobalt enriched by the oxidation method and the purifying agent are higher than the cobalt extracted by the method without further enriched cobalt (the cobalt residue contains only about 2% of cobalt).
In addition, in example 1 and the comparative experiment, the requirements for liquid components are different, wherein the oxidation method requires that the manganese content in the solution is low enough (5 g/L of manganese ions are contained in the zinc electrolysis waste liquid, manganese dioxide is produced after potassium permanganate is added, and cobalt slag contains a large amount of manganese dioxide, so that the cobalt content of the cobalt slag is low), therefore, the manganese in the zinc electrolysis waste liquid needs to be treated in advance, so that the production cost is increased, and the novel purifying agent does not have the requirement for the manganese ion, so that the production cost is reduced.
Other alternative embodiments of the invention will not be described in detail herein.
Compared with the existing cobalt precipitation scheme by oxidation, the cobalt precipitation by the new purifying agent and the new purifying agent are both firstly to the Co in the solution2+The oxidation is carried out firstly, the difference is that the complexation method is different, and the product adopting the novel purifying agent is Co (R-NS)2)3↓, the product of oxidation is CoOOH. The cadmium recovered waste alkali liquid zinc oxide calcine is used to regulate pH value, so that it can save cost compared with other neutralizing agents. By bakingBaking is adopted for drying, so that the water transportation cost in the selling process is greatly reduced.
While embodiments of the invention have been described above, it is not limited to the applications set forth in the description and the embodiments, which are fully applicable in various fields of endeavor to which the invention pertains, and further modifications may readily be made by those skilled in the art, it being understood that the invention is not limited to the details shown and described herein without departing from the general concept defined by the appended claims and their equivalents.
Claims (10)
1. A method for extracting cobalt from a cadmium-poor high-cobalt liquid is characterized by comprising the following steps:
adding zinc powder into the low-cadmium high-cobalt solution, and reacting and filtering to obtain a cadmium-removed solution;
adding hydrogen peroxide and zinc oxide into the cadmium-removed solution, reacting and filtering to obtain iron-removed solution;
adding a purifying agent and an activating agent into the iron-removed liquid to obtain a cobalt ion precipitate;
mixing the cobalt ion precipitate with waste electrolyte for reaction to obtain acid-washed cobalt slag;
and washing and baking the acid-washed cobalt slag to obtain the high-cobalt slag dry slag.
2. The method for extracting cobalt from the cadmium-depleted cobalt-rich solution according to claim 1, wherein the adding zinc powder into the cadmium-depleted cobalt-rich solution, and obtaining the cadmium-removed solution after reaction and filtration specifically comprises:
adding zinc powder into the cadmium-poor high cobalt solution at the temperature of 45-60 ℃, reacting for 0.7-1.0h, and performing filter pressing to obtain cadmium slag and cadmium-removed solution;
wherein the weight ratio of the zinc powder to the cadmium in the cadmium-poor cobalt-rich liquid is 2-4: 1.
3. The method for extracting cobalt from the cadmium-depleted high-cobalt liquid as claimed in claim 1, wherein the step of adding hydrogen peroxide and zinc oxide into the cadmium-removed liquid, and the step of reacting and filtering to obtain the iron-removed liquid specifically comprises the steps of:
adding hydrogen peroxide and zinc oxide into the cadmium-removed solution at the temperature of 60-70 ℃, reacting for 1.0-1.5h, adjusting the pH to 2.5, adding whiting powder, and adjusting the pH to 2.7-3.7;
and adding a flocculating agent, and performing solid-liquid separation to obtain iron-removed liquid and iron slag.
4. The method for extracting cobalt from the cadmium-depleted and cobalt-enriched liquid as claimed in claim 3, wherein the weight ratio of the water dioxide and the iron is 1.5-2.0:1, and the initial adding weight of the whiting powder is 0.5 times of the weight of the hydrogen peroxide.
5. The method for extracting cobalt from the cadmium-depleted cobalt-rich liquid as claimed in claim 1, wherein the step of adding a purifying agent and an activating agent to the iron-removed liquid to obtain a cobalt ion precipitate specifically comprises:
adding a purifying agent 3R-NS and an activating agent at 70-80 ℃, and reacting for 1.0-2.0h to obtain a cobalt ion precipitate Co (R-NS)2)3。
6. The method for extracting cobalt from the cadmium-depleted high cobalt liquid as claimed in claim 5, wherein the weight ratio of the purifying agent to the cobalt in the iron-removed liquid is 20:1, and the weight ratio of the activating agent to the purifying agent is 0.1: 1.
7. The method for extracting cobalt from the cadmium-depleted cobalt-rich solution according to claim 1, wherein the step of mixing the cobalt ion precipitate with the waste electrolyte to obtain the acid-washed cobalt residue specifically comprises:
precipitating the cobalt ion into Co (R-NS)2)3Mixing with water, adding waste electrolyte, and pickling at 60-70 deg.C for 1.5-2.0 hr to obtain pickling solution;
and adjusting the pH value of the pickling solution to 0.5-1.0, and performing filter pressing to obtain pickled cobalt slag and a zinc-containing solution.
8. The method of claim 7, wherein the cadmium-depleted cobalt solution is obtained fromMethod for extracting cobalt, characterized in that the cobalt ion precipitate Co (R-NS)2)3The weight ratio of the waste electrolyte to water is 3-5:1, and the waste electrolyte contains 140-160g/L of acid.
9. The method for extracting cobalt from the cadmium-poor high cobalt solution according to claim 7, wherein the washing and baking of the acid-washed cobalt slag to obtain the high cobalt slag dry slag specifically comprises:
when acid-washed cobalt slag is obtained through filter pressing, clear water at the temperature of 70-75 ℃ is directly added to the acid-washed cobalt slag to wash the acid-washed cobalt slag on a filter press for 2-3 times, and the acid-washed cobalt slag is obtained through filter pressing;
and baking the washed cobalt slag in a baking furnace to obtain the high-cobalt slag dry slag.
10. The method for extracting cobalt from the cadmium-poor cobalt-rich liquid as claimed in any one of claims 1 to 9, wherein the method further comprises the following steps of adding zinc powder into the cadmium-poor cobalt-rich liquid, and obtaining cadmium slag and cadmium-removed liquid after reaction and filtration:
pulping nickel-cobalt slag and water, adding zinc electrolysis waste liquid, reacting for 2-3h at 75-80 ℃, adjusting the pH value to 5.0, and filtering to obtain the cadmium-poor high-cobalt liquid.
Wherein the volume ratio of the nickel-cobalt slag to the water is 3-5:1, and the zinc electrolyte contains 140-160g/L of acid.
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