CN112921174B - Method for hydrometallurgical preparation of cobalt intermediate product - Google Patents

Method for hydrometallurgical preparation of cobalt intermediate product Download PDF

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CN112921174B
CN112921174B CN202110080981.5A CN202110080981A CN112921174B CN 112921174 B CN112921174 B CN 112921174B CN 202110080981 A CN202110080981 A CN 202110080981A CN 112921174 B CN112921174 B CN 112921174B
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cobalt
solution
organic phase
resin
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CN112921174A (en
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王从泽
曹栋强
龚丽锋
王红忠
黄飞中
罗瑞平
邱颖
任红霞
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Zhejiang Gepai Cobalt Industry New Material Co ltd
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Zhejiang Gepai Cobalt Industry New Material Co ltd
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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
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
    • C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
    • C22B3/08—Sulfuric acid, other sulfurated acids or salts thereof
    • 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
    • C22B23/0407—Leaching processes
    • C22B23/0415—Leaching processes with acids or salt solutions except ammonium salts solutions
    • C22B23/043—Sulfurated acids or salts thereof
    • 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
    • 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
    • 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
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/22—Treatment or purification of solutions, e.g. obtained by leaching by physical processes, e.g. by filtration, by magnetic means, or by thermal decomposition
    • C22B3/24—Treatment or purification of solutions, e.g. obtained by leaching by physical processes, e.g. by filtration, by magnetic means, or by thermal decomposition by adsorption on solid substances, e.g. by extraction with solid resins
    • 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
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
    • 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

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Abstract

The invention relates to a preparation process of a cobalt product, in particular to a method for hydrometallurgical preparation of a cobalt intermediate product. A method for hydrometallurgical preparation of a cobalt intermediate product comprises the following steps: (1) a leaching process; (2) iron removal process; (3) an extraction separation process; (4) removing oil; and (5) an evaporation crystallization process. The invention provides a method for hydrometallurgical preparation of a cobalt intermediate product, which can prolong the oil removal time of resin and reduce the backwashing frequency, thereby improving the working efficiency and effectively reducing the oil content in a cobalt-containing aqueous solution.

Description

Method for hydrometallurgical preparation of cobalt intermediate product
Technical Field
The invention relates to a preparation process of a cobalt product, in particular to a method for hydrometallurgical preparation of a cobalt intermediate product.
Background
In the process of extracting cobalt by using kerosene as a solvent and P507 as an extracting agent in a cobalt-containing intermediate hydrometallurgy process, the oil content in a subsequent cobalt-containing aqueous solution is high. Therefore, the oil content in the subsequent cobalt-containing aqueous solution can be effectively reduced, which is the key for improving the product quality. At present, the most effective degreasing method is to remove oil by resin adsorption, and although resin degreasing can effectively reduce oil in the product, the amount of oil adsorbed by resin is limited, and after a certain amount of oily water solution is treated, the resin is easily saturated, so that the function of adsorbing oil is lost, and at this time, the resin needs to be backwashed, so that the oil in the resin is reduced. However, frequent backwashing of the resin can severely reduce the efficiency of operation, and backwashing can also generate large amounts of wastewater. Therefore, it is important to develop a process for reducing the number of resin backwashes.
Disclosure of Invention
Aiming at the problems, the invention provides a method for hydrometallurgical smelting of a cobalt intermediate product, which can prolong the oil removal time of resin and reduce the backwashing frequency, thereby improving the working efficiency and effectively reducing the oil content in a cobalt-containing aqueous solution.
The invention discloses a method for hydrometallurgical preparation of a cobalt intermediate product, which can be realized by the following technical scheme:
a method for hydrometallurgical preparation of a cobalt intermediate product comprises the following steps:
(1) Leaching process
a. Adding water and a cobalt intermediate into a leaching tank according to a solid-to-liquid ratio of (1 to 5) 1, adding 98 percent concentrated sulfuric acid into the tank under the conditions of normal temperature and normal pressure until the pH value of slurry is 1.0 to 1.8, and then adding H 2 O 2 Until the cobalt intermediate product is completely dissolved, the pH value needs to be maintained at 1.0-1.8 in the whole process, and the temperature is maintained at 60-70 ℃ in the whole process;
(2) Iron removal process
a. Adding carbonate into the leachate obtained in the step 1 to adjust the pH value to 3.0-4.0, and maintaining the temperature in the whole process at 60-70 ℃;
b. filtering;
(3) Extraction separation process
i. P204 extraction and impurity removal process
a. Saponification: saponifying the organic phase by using alkali to obtain a saponified organic phase;
b. extraction: extracting impurities (calcium, copper, zinc, manganese, iron, aluminum and the like) in the iron-removed liquid into an organic phase by using a saponified organic phase to obtain a loaded organic phase (containing impurities) and P204 raffinate; carrying out oil separation treatment on the P204 raffinate, and then entering a P507 cobalt extraction process;
c. washing: washing the loaded organic phase (containing impurities) by using acid liquor generated in an acid washing process;
d. back extraction: carrying out back extraction on the washed loaded organic phase (containing impurities) by using hydrochloric acid to obtain copper-manganese liquid;
ii. P507 cobalt extraction process
a. Extraction: fully mixing the saponified organic phase with P204 raffinate, and allowing cobalt in the solution to enter the organic phase to obtain a loaded organic phase (containing cobalt);
b. washing: washing the loaded organic phase (containing cobalt) with hydrochloric acid;
c. back extraction: carrying out back extraction on the washed loaded organic phase (containing cobalt) by using sulfuric acid to obtain a qualified cobalt sulfate solution;
(4) Oil removal
a. Aeration oil removal
Carrying out aeration treatment on the qualified cobalt sulfate solution obtained in the step 3, wherein the aeration time is 2 to 5 hours;
b. standing still
Standing at room temperature for 0.5 to 20 hours after the aeration is finished, taking out the upper layer solution after the standing is finished, continuously carrying out aeration oil removal treatment, and carrying out resin oil removal treatment on the lower layer solution;
c. resin degreasing
Taking out the lower layer solution, and dripping the lower layer solution from top to bottom through an adsorption column filled with resin at a flow rate of 1-10mL/min;
(5) Evaporative crystallization process
a. Pumping the deoiled cobalt sulfate solution into an evaporation chamber by using a pump, opening a steam switch to introduce steam into the evaporation chamber, and flowing the concentrated solution into a crystallization tank;
b. placing the hot cobalt sulfate concentrated solution in a tank, starting stirring, and opening cooling water for cooling; with the stirring, the solution is gradually cooled, and the cobalt sulfate concentrated solution is supersaturated and crystallized; and (4) putting the cobalt sulfate crystals into a centrifuge for solid-liquid separation, drying and packaging to obtain a cobalt sulfate product.
The volume of the oil-containing cobalt sulfate aerated in the step (4) a is 10L.
And (4) the air inlet pipe used for aeration in the step (4) a extends into the bottom of the solution.
The aeration time in the step (4) a is 3.5h.
The standing time in the step (4) b is 15h.
The flow rate in the step (4) c is 5-10mL/min.
The adsorption column in the step (4) c is an adsorption column with the diameter of 10x1000 mm.
The volume of the resin in the step (4) c is 1/2 to 1/3 of the volume of the adsorption column.
The lower layer solution in the step (4) c passes through the adsorption column filled with the resin in a top-down manner.
The resin in the step (4) c is one or two of OA-01 resin, SD-300 resin or ORZ-05 resin.
In the aeration oil removal process of the process, the aeration can separate the oil from the stock solution with the oil content of 24.568mg/L, the oil content of the separated solution is 20.768mg/L, and the oil content of the lower layer is 5.13mg/L. After the solution with low oil content in the lower layer passes through the adsorption column filled with resin, the oil content in the solution can be reduced to 1mg/L.
The invention has the following beneficial effects:
(a) In the wet smelting process of the cobalt intermediate product, the oil content in the cobalt product is high through an extraction process, the solution oil content of the lower layer of the oil-containing solution can be low and the solution oil content of the upper layer of the oil-containing solution can be high through an aeration oil removal mode, and then the solution with the low oil content of the lower layer is adsorbed and removed through resin, so that the oil content in the solution can be reduced to 1mg/L. (b) Because the oil content of the oil-containing solution passing through the resin is low, the time for the resin to reach saturation is longer, the service time of the resin is longer, the backwashing frequency is reduced, the work efficiency is improved, and the industrial wastewater caused by backwashing can be reduced. (c) The aeration mode is adopted for oil removal, new impurities cannot be introduced into the oil removal process, and the process is more green and environment-friendly.
Drawings
FIG. 1 is a schematic process flow diagram of a method for removing oil from an aqueous solution containing cobalt according to the present invention;
FIG. 2 is a graph showing the relationship between aeration time and lower oil content in the method for removing oil from an aqueous solution containing cobalt according to the present invention;
FIG. 3 is a diagram showing the relationship between the oil removal time of the resin and the oil content of the solution in the method for removing oil from an aqueous solution containing cobalt.
Detailed Description
Example 1
Step 1: and (3) leaching:
a. adding water and a cobalt intermediate into a leaching tank according to a solid-to-liquid ratio of (1 to 5) 1, adding 98 percent concentrated sulfuric acid into the tank under the conditions of normal temperature and normal pressure until the pH value of slurry is 1.0 to 1.8, and then adding H 2 O 2 Until the cobalt intermediate product is completely dissolved, the pH value needs to be maintained at 1.0-1.8 in the whole process, and the temperature is maintained at 60-70 ℃ in the whole process.
Step 2: iron removal process:
a. adding carbonate into the leachate obtained in the step 1 to adjust the pH value to 3.0-4.0, and maintaining the temperature at 60-70 ℃ in the whole process.
b. Filtration
And step 3: extractive separation process
1. P204 extraction and impurity removal:
a. saponification: saponifying the organic phase by using alkali to obtain a saponified organic phase;
b. extraction: extracting impurities (calcium, copper, zinc, manganese, iron, aluminum and the like) in the iron-removed liquid into an organic phase by using a saponified organic phase to obtain a loaded organic phase (containing impurities) and P204 raffinate; the P204 raffinate is subjected to oil removal treatment and then enters a P507 cobalt extraction process;
c. washing: washing the loaded organic phase (containing impurities) by using acid liquor generated in an acid washing process;
d. back extraction: and (4) carrying out back extraction on the washed loaded organic phase (containing impurities) by using hydrochloric acid to obtain the copper-manganese liquid.
2. P507 cobalt extraction process:
a. and (3) extraction: fully mixing the saponified organic phase with the P204 raffinate, and enabling cobalt in the solution to enter the organic phase to obtain a loaded organic phase (containing cobalt);
b. washing: washing the loaded organic phase (containing cobalt) with hydrochloric acid;
c. back extraction: carrying out back extraction on the washed loaded organic phase (containing cobalt) by using sulfuric acid to obtain a qualified cobalt sulfate solution;
and 4, step 4: oil removal
a. Aeration oil removal
Taking 10L of the qualified cobalt sulfate solution obtained in the step 3, and carrying out aeration treatment, wherein the oil content of the qualified cobalt sulfate solution is 24.586mg/L, and the aeration time is 3 hours;
b. standing still
Standing at room temperature for 17 hr after aeration, taking out the upper layer solution (oil content of 17.693 mg/L), and performing aeration oil removal treatment, and performing resin oil removal treatment on the lower layer solution (oil content of 10.168 mg/L);
c. resin degreasing
Taking out the solution at the middle-lower layer of 2, dripping the solution from top to bottom through an adsorption column filled with resin at the flow rate of 5mL/min, wherein the size of the adsorption column is phi 10x1000mm, the height of the adsorption column is 40cm, suqing OA-01 resin is filled in the adsorption column, the volume of the cobalt sulfate solution after passing through the resin is 4L, and the oil content is 5.585mg/L.
And 5: and (3) an evaporation crystallization process:
a. pumping the deoiled cobalt sulfate solution into an evaporation chamber by using a pump, opening a steam switch to introduce steam into the evaporation chamber, and flowing the concentrated solution into a crystallization tank.
b. Placing the hot cobalt sulfate concentrated solution in a tank, starting stirring, and opening cooling water for cooling; with the stirring, the solution is gradually cooled, and the cobalt sulfate concentrated solution is supersaturated and crystallized; and (3) putting the cobalt sulfate crystals into a centrifuge for solid-liquid separation, drying and packaging into a cobalt sulfate product, wherein the oil content of the obtained cobalt sulfate product is 2.13ppm.
Example 2
Step 1: and (3) leaching:
a. adding water and a cobalt intermediate into a leaching tank according to a solid-to-liquid ratio of (1 to 5) 1, adding 98 percent concentrated sulfuric acid into the tank under the conditions of normal temperature and normal pressure until the pH value of slurry is 1.0 to 1.8, and then adding H 2 O 2 Until the cobalt intermediate is completely dissolved, the pH value needs to be maintained in the whole process1.0-1.8, and the temperature in the whole process is maintained at 60-70 ℃.
And 2, step: iron removal process:
a. adding carbonate into the leachate obtained in the step 1 to adjust the pH value to 3.0-4.0, and maintaining the temperature of the whole process at 60-70 ℃.
b. Filtration
And step 3: extraction separation process
1. P204 extraction and impurity removal process:
a. saponification: saponifying the organic phase by using alkali to obtain a saponified organic phase;
b. and (3) extraction: extracting impurities (calcium, copper, zinc, manganese, iron, aluminum and the like) in the iron-removed liquid into an organic phase by using a saponified organic phase to obtain a loaded organic phase (containing impurities) and P204 raffinate; the P204 raffinate is subjected to oil removal treatment and then enters a P507 cobalt extraction process;
c. washing: washing the loaded organic phase (containing impurities) by using acid liquor generated in an acid washing process;
d. back extraction: and (4) carrying out back extraction on the washed loaded organic phase (containing impurities) by using hydrochloric acid to obtain the copper-manganese liquid.
2. P507 cobalt extraction process:
a. and (3) extraction: fully mixing the saponified organic phase with the P204 raffinate, and enabling cobalt in the solution to enter the organic phase to obtain a loaded organic phase (containing cobalt);
b. washing: washing the loaded organic phase (containing cobalt) with hydrochloric acid;
c. back extraction: carrying out back extraction on the washed loaded organic phase (containing cobalt) by using sulfuric acid to obtain a qualified cobalt sulfate solution;
and 4, step 4: oil removal
a. Aeration oil removal
Taking 10L of the qualified cobalt sulfate solution obtained in the step 3, and carrying out aeration treatment, wherein the oil content of the qualified cobalt sulfate solution is 24.586mg/L, and the aeration time is 3.5 hours;
b. standing still
Standing at room temperature for 15 hr after aeration, taking out the upper layer solution (with oil content of 20.768 mg/L), and performing aeration oil-removing treatment, and performing resin oil-removing treatment on the lower layer solution (with oil content of 5.13 mg/L);
c. resin degreasing
Taking out the solution at the middle-lower layer of 2, dripping the solution from top to bottom through an adsorption column filled with resin at the flow rate of 5mL/min, wherein the size of the adsorption column is phi 10x1000mm, the height of the adsorption column is 40cm, suqing OA-01 resin is filled in the adsorption column, the volume of the cobalt sulfate solution after passing through the resin is 4L, and the oil content is 1mg/L.
And 5: and (3) an evaporation crystallization process:
a. pumping the deoiled cobalt sulfate solution into an evaporation chamber by using a pump, opening a steam switch to introduce steam into the evaporation chamber, and flowing the concentrated solution into a crystallization tank.
b. Placing the hot cobalt sulfate concentrated solution in a tank, starting stirring, and opening cooling water for cooling; with the stirring, the solution is gradually cooled, and the cobalt sulfate concentrated solution is supersaturated and crystallized; and (3) putting the cobalt sulfate crystals into a centrifuge for solid-liquid separation, drying and packaging into a cobalt sulfate product, wherein the oil content of the obtained cobalt sulfate product is 1.13ppm.
Example 3
Step 1: and (3) leaching:
a. adding water and a cobalt intermediate into a leaching tank according to the solid-to-liquid ratio of (1 to 5) 1, respectively, adding 98 percent concentrated sulfuric acid into the tank under the conditions of normal temperature and normal pressure until the pH of slurry is 1.0-1.8, and then adding H 2 O 2 Until the cobalt intermediate product is completely dissolved, the pH value needs to be maintained at 1.0-1.8 in the whole process, and the temperature is maintained at 60-70 ℃ in the whole process.
Step 2: iron removal process:
a. adding carbonate into the leachate obtained in the step 1 to adjust the pH value to 3.0-4.0, and maintaining the temperature at 60-70 ℃ in the whole process.
b. Filtration
And 3, step 3: extraction separation process
1. P204 extraction and impurity removal process:
a. saponification: saponifying the organic phase by using alkali to obtain a saponified organic phase;
b. and (3) extraction: extracting impurities (calcium, copper, zinc, manganese, iron, aluminum and the like) in the iron-removed liquid into an organic phase by using a saponified organic phase to obtain a loaded organic phase (containing impurities) and P204 raffinate; carrying out oil separation treatment on the P204 raffinate, and then entering a P507 cobalt extraction process;
c. washing: washing the loaded organic phase (containing impurities) by using acid liquor generated in an acid washing process;
d. back extraction: and (4) carrying out back extraction on the washed loaded organic phase (containing impurities) by using hydrochloric acid to obtain the copper-manganese solution.
2. P507 cobalt extraction process:
a. and (3) extraction: fully mixing the saponified organic phase with the P204 raffinate, and enabling cobalt in the solution to enter the organic phase to obtain a loaded organic phase (containing cobalt);
b. washing: washing the loaded organic phase (containing cobalt) with hydrochloric acid;
c. back extraction: carrying out back extraction on the washed loaded organic phase (containing cobalt) by using sulfuric acid to obtain a qualified cobalt sulfate solution;
and 4, step 4: oil removal
a. Aeration oil removal
Taking 10L of the qualified cobalt sulfate solution obtained in the step 3, and carrying out aeration treatment, wherein the oil content of the qualified cobalt sulfate solution is 24.586mg/L, and the aeration time is 3 hours;
b. standing still
Standing at room temperature for 16.5 hr after aeration, taking out the upper layer solution (with oil content of 22.872 mg/L), and performing aeration oil-removing treatment, and performing resin oil-removing treatment on the lower layer solution (with oil content of 16.222 mg/L);
c. resin degreasing
Taking out the solution at the middle-lower layer of 2, dripping the solution from top to bottom through an adsorption column filled with resin at a flow rate of 5mL/min, wherein the size of the adsorption column is phi 10x1000mm, the height of the adsorption column is 40cm, suqing OA-01 resin is filled in the adsorption column, the volume of the cobalt sulfate solution after passing through the resin is 4L, and the oil content is 6.282mg/L.
And 5: and (3) an evaporation crystallization process:
a. pumping the deoiled cobalt sulfate solution into an evaporation chamber by using a pump, opening a steam switch to introduce steam into the evaporation chamber, and flowing the concentrated solution into a crystallization tank.
b. Placing the hot cobalt sulfate concentrated solution in a tank, starting stirring, and opening cooling water for cooling; with the stirring, the solution is gradually cooled, and the cobalt sulfate concentrated solution is supersaturated and crystallized; and (3) putting the cobalt sulfate crystals into a centrifuge for solid-liquid separation, drying and packaging into a cobalt sulfate product, wherein the oil content of the obtained cobalt sulfate product is 4.13ppm.
Secondly, the applicant studies the relationship between the aeration time and the lower oil content, and obtains the attached figure 2, and it can be seen from the figure that the aeration time has a great influence on the result, and the oil content is only 5mg/L at the time of 3.5 hours.
The applicant also studied the relationship between the resin degreasing time and the solution oil content and obtained fig. 3, from which it can be seen that the relationship between the resin degreasing time and the solution oil content is not as long as possible but almost opposite, and therefore the time can be saved while obtaining a better product.
The above embodiments are only intended to illustrate the technical solution of the present invention and not to limit the same, and those skilled in the art can make various corresponding changes and modifications according to the present invention without departing from the spirit and the essence of the present invention, but those corresponding changes and modifications should fall within the scope of the appended claims.

Claims (1)

1. The method for the cobalt intermediate hydrometallurgy is characterized by comprising the following steps:
(1) Leaching process
a. Adding water and a cobalt intermediate into a leaching tank according to a solid-to-liquid ratio of (1 to 5) 1, adding 98 percent concentrated sulfuric acid into the tank under the conditions of normal temperature and normal pressure until the pH value of slurry is 1.0 to 1.8, and then adding H 2 O 2 Until the cobalt intermediate product is completely dissolved, the pH value needs to be maintained at 1.0-1.8 in the whole process, and the temperature is maintained at 60-70 ℃ in the whole process;
(2) Iron removal process
a. Adding carbonate into the leachate obtained in the step 1 to adjust the pH value to 3.0-4.0, and maintaining the temperature in the whole process at 60-70 ℃;
b. filtering;
(3) Extraction separation process
i. P204 extraction and impurity removal process
a. Saponification: saponifying the organic phase by using alkali to obtain a saponified organic phase;
b. extraction: extracting impurities in the iron-removed liquid into an organic phase by using a saponified organic phase to obtain a loaded organic phase and P204 raffinate; the P204 raffinate is subjected to oil removal treatment and then enters a P507 cobalt extraction process;
c. washing: washing the loaded organic phase with acid solution generated in an acid washing process;
d. back extraction: carrying out back extraction on the washed loaded organic phase by using hydrochloric acid to obtain copper-manganese liquid;
ii. P507 cobalt extraction process
a. And (3) extraction: fully mixing the saponified organic phase with P204 raffinate, and allowing cobalt in the solution to enter the organic phase to obtain a loaded organic phase;
b. washing: washing the loaded organic phase with hydrochloric acid;
c. back extraction: carrying out back extraction on the washed loaded organic phase by using sulfuric acid to obtain a qualified cobalt sulfate solution;
(4) Oil removal
a. Aeration oil removal
Carrying out aeration treatment on the qualified cobalt sulfate solution obtained in the step 3, wherein the aeration time is 2 to 5 hours;
b. standing still
Standing at room temperature after the aeration is finished, wherein the standing time is 0.5 to 20 hours, taking out the upper-layer solution after the standing is finished, continuously performing aeration oil removal treatment, and performing resin oil removal treatment on the lower-layer solution;
c. resin degreasing
Taking out the lower layer solution, and dripping the lower layer solution from top to bottom through an adsorption column filled with resin at a flow rate of 1-10mL/min;
(5) Evaporative crystallization process
a. Pumping the deoiled cobalt sulfate solution into an evaporation chamber by using a pump, opening a steam switch to introduce steam into the evaporation chamber, and flowing the concentrated solution into a crystallization tank;
b. placing the hot cobalt sulfate concentrated solution in a tank, starting stirring, and opening cooling water for cooling; with the stirring, the solution is gradually cooled, and the cobalt sulfate concentrated solution is supersaturated and crystallized; putting the cobalt sulfate crystals into a centrifuge for solid-liquid separation, drying and then packaging into a cobalt sulfate product;
the volume of the oil-containing cobalt sulfate aerated in the step (4) a is 10L; the air inlet pipe used for aeration in the step (4) a extends into the bottom of the solution; the aeration time in the step (4) a is 3.5h; the standing time in the step (4) b is 15h; the flow rate in the step (4) c is 5-10mL/min; the adsorption column in the step (4) c is an adsorption column with the diameter of phi 10x1000 mm; the volume of the resin in the step (4) c is 1/2 to 1/3 of the volume of the adsorption column; the lower layer solution in the step (4) c passes through an adsorption column filled with resin from top to bottom; the resin in the step (4) c is one or two of OA-01 resin, SD-300 resin or ORZ-05 resin.
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