CN113957249B - Method for separating zinc and cobalt ions in solution - Google Patents

Method for separating zinc and cobalt ions in solution Download PDF

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CN113957249B
CN113957249B CN202110064638.1A CN202110064638A CN113957249B CN 113957249 B CN113957249 B CN 113957249B CN 202110064638 A CN202110064638 A CN 202110064638A CN 113957249 B CN113957249 B CN 113957249B
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cobalt
solution
zinc
cobalt ions
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CN113957249A (en
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黄宇坤
曹亦俊
范桂侠
彭伟军
白宁宁
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Zhengzhou University
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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
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/006—Wet processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
    • B03D1/00—Flotation
    • 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
    • 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 discloses a method for separating zinc and cobalt ions in a solution, belongs to the technical field of cobalt recovery, and solves the problems of low and incomplete separation efficiency of zinc and cobalt ions in the prior art. Comprising the following steps: step 1, adjusting the pH value of a solution containing zinc and cobalt ions to be acidic through a pH regulator; step 2, simultaneously adding a cobalt ion chelating precipitant and a particle stabilizer into the solution at a certain temperature, and stirring and mixing to obtain a first intermediate system; the first intermediate system is a solution containing cobalt ion chelating precipitation particles; step 3, adding a surfactant into the first intermediate system, and stirring and uniformly mixing to obtain a second intermediate system; the second intermediate system is a suspension containing cobalt precipitation suspended particles; and 4, performing aerated flotation on the second intermediate system by adopting a flotation separation device, and collecting particles containing cobalt precipitate. The method of the invention effectively solves the difficult problem of zinc and cobalt separation.

Description

Method for separating zinc and cobalt ions in solution
Technical Field
The invention belongs to the technical field of cobalt recovery, and particularly relates to a method for separating zinc and cobalt ions in a solution.
Background
Cobalt is a strategic metal resource that supports the development of the high technology field. Along with popularization of electronic products and popularization of new energy automobiles, cobalt is increasingly widely applied to battery materials, and the demand of cobalt is also increasing. However, global cobalt reserves are only around 700 ten thousand tons, and the distribution is relatively concentrated. The reserves in China only account for 1.1% of the global reserves, and most of the reserves are associated with sulfide ores of metals such as zinc, copper, nickel and the like, so that the direct smelting and extraction of cobalt-containing minerals is difficult, high in cost and difficult to meet the rapidly growing cobalt consumption demands in China. Therefore, development of separation and extraction technology of various cobalt-containing resources (cobalt-containing solid waste, industrial wastewater and the like) is a necessary task for guaranteeing cobalt raw material supply.
Smelting slag containing zinc and cobalt, industrial solid waste and waste battery materials are important secondary resources containing cobalt, and metal components can enter the leaching solution through an acid leaching process; in addition, zinc cobalt ions exist in a certain concentration in a part of industrial wastewater. The separation and extraction of cobalt in the secondary resource containing zinc and the purification and impurity removal of cobalt in the solution are both required to face the problem of high-efficiency separation of zinc and cobalt ions in the solution, namely a separation reagent and a method with high selectivity for cobalt ions in the solution are required.
At present, the separation method of zinc and cobalt in the solution mainly comprises a zinc powder replacement method, an extraction method, a precipitation method and the like. The zinc powder replacement method needs a large amount of zinc powder, and realizes the reduction of cobalt in the solution and the formation of precipitate by utilizing the potential difference of zinc and cobalt; however, the method needs to add zinc powder of which the theoretical amount is tens times higher, and the formed cobalt-removed slag contains a large amount of unreacted zinc powder, so that the extraction of cobalt in the cobalt-removed slag is again subjected to the problem of zinc-cobalt separation. When a solvent extraction method is adopted to separate zinc and cobalt in the solution, the extraction effect is poor because the content of cobalt ions in the solution is generally low; meanwhile, when zinc and cobalt in the solution are separated by adopting a precipitation method, the available precipitants comprise sulfides, xanthates and the like, but are also influenced by low cobalt ion content, so that larger precipitated particles are difficult to form, the sedimentation process is slow, and the complete separation is difficult.
The method for separating zinc and cobalt ions in the solution is limited by the problems of poor selectivity, low separation efficiency, incomplete separation and the like caused by low concentration of cobalt ions in the solution. Therefore, how to efficiently separate zinc and cobalt ions in a solution is a problem to be solved.
Disclosure of Invention
In view of the analysis, the invention aims to provide a method for separating zinc and cobalt ions in a solution, which is used for solving the problems of poor selectivity, low separation efficiency and incomplete separation caused by low concentration of cobalt ions in the solution in the prior art and can realize high-efficiency separation of zinc and cobalt ions in the solution.
The aim of the invention is mainly realized by the following technical scheme:
the invention provides a method for separating zinc and cobalt ions in a solution, which comprises the following steps:
step 1, adjusting the pH value of a solution containing zinc and cobalt ions to be acidic through a pH regulator;
step 2, simultaneously adding a cobalt ion chelating precipitant and a particle stabilizer into the solution at a certain temperature, and stirring and mixing to obtain a first intermediate system; the first intermediate system is a solution containing cobalt ion chelating precipitation particles;
step 3, adding a surfactant into the first intermediate system, and stirring and uniformly mixing to obtain a second intermediate system; the second intermediate system is a suspension containing cobalt precipitation suspended particles;
and 4, performing aerated flotation on the second intermediate system by adopting a flotation separation device, and collecting particles containing cobalt precipitate.
In the step 1, the concentration of zinc ions in the solution containing zinc and cobalt ions is 0.5-185 g/L, and the concentration of cobalt ions is 1 mg/L-5 g/L.
Further, in the step 1, the pH of the adjusted solution is 4.5 to 6.0.
Further, in the step 2, the temperature is 20 to 50 ℃.
Further, in the step 2, the cobalt ion chelating precipitant is one or a mixture of sodium ethyl xanthate and potassium ethyl xanthate.
Further, in the step 2, the molar ratio of the addition amount of the cobalt ion chelating precipitant to the cobalt ions in the solution is 4:1-10:1.
Further, in the step 2, the particle stabilizer includes anhydrous copper sulfate and/or hydrous copper sulfate.
Further, in the step 2, the molar ratio of the addition amount of the particle stabilizer to cobalt ions in the solution is 1:1-3:1.
In step 2, the stirring speed is less than or equal to 100rpm, and the stirring time is 10-60 min.
Further, in the step 3, the particle diameter of the suspended particles is 20 to 50. Mu.m.
Compared with the prior art, the invention can at least realize one of the following technical effects:
1) The invention applies the chelate precipitation-floatation method to the separation of zinc and cobalt ions in the solution for the first time, utilizes the selective complexation of the cobalt ion chelate precipitant to selectively chelate the cobalt ions in the solution, and enables the chelate of the cobalt ions and the medicament to form suspended particles through the particle stabilizer added simultaneously, and finally realizes the selective extraction of the cobalt ions in the solution by virtue of the microbubble floatation technology, thereby achieving the purpose of efficiently separating the zinc and the cobalt ions in the solution. The method can be used for separating zinc and cobalt ions and removing cobalt ions from various solutions containing low-concentration cobalt ions, and has the advantages of good zinc and cobalt separation effect, high cobalt ion recovery rate, low cost and short flow.
2) The existing zinc-cobalt separation technology comprises a zinc powder replacement method, a xanthate cobalt removal method and an alpha-nitroso-beta-naphthol cobalt removal method. Zinc powder displacement method: the zinc powder consumption is large, generally more than 20 times of theoretical amount, the operation time is long, the zinc powder needs to be carried out at about 80 ℃, and AsH is often generated 3 And SbH 3 Toxic gas. Cobalt removal method for xanthate: because the concentration of cobalt ions in the solution is low, excessive xanthate must be added to enable the reaction to be rapidly carried out and the cobalt to be thoroughly removed, and the dosage is generally 10-15 times of the theoretical dosage. Cobalt removal method for alpha-nitroso-beta-naphthol: the method has the same defects as the method for removing cobalt from xanthate, and has large dosage of medicament, and in order to ensure the quality of the purified liquid electrolysis, the active carbon is required to be adopted to adsorb excessive organic medicament in the leaching liquid. Compared with the existing method, the method has wide application range of the concentration of the metal ions in the solution, particularly has stronger applicability in the aspect of removing the low-concentration ions, and has low reagent dosage; can be continuously carried out, has large solution treatment capacity, high solid-liquid separation rate and more thorough metal ion separation.
Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. The objectives and other advantages of the invention will be realized and attained by the structure particularly pointed out in the written description and drawings.
Drawings
The drawings are only for purposes of illustrating particular embodiments and are not to be construed as limiting the invention, like numbers referring to like parts throughout the drawings.
FIG. 1 is a process flow diagram of the separation method of the present invention.
Detailed Description
The following describes in further detail a method for separating zinc and cobalt ions from a solution with reference to specific examples, which are for comparison and explanation purposes only, and the present invention is not limited to these examples.
A method for separating zinc and cobalt ions in a solution comprises the following steps:
step 1, adjusting the pH value of a solution containing zinc and cobalt ions to be acidic through a pH regulator;
step 2, simultaneously adding a cobalt ion chelating precipitant and a particle stabilizer into the solution at a certain temperature, and stirring and mixing to obtain a first intermediate system; the first intermediate system is a solution containing cobalt ion chelating precipitation particles;
step 3, adding a surfactant into the first intermediate system, and stirring and uniformly mixing to obtain a second intermediate system; the second intermediate system is a suspension containing cobalt precipitation suspended particles;
and 4, performing air flotation on the second intermediate system by adopting a flotation separation device, collecting particles containing cobalt precipitates, and realizing selective chelate precipitation-flotation removal of cobalt ions in the solution and high-efficiency separation of zinc and cobalt.
Specifically, in the step 1, the solution containing zinc and cobalt ions may be zinc hydrometallurgy leaching solution, or acid leaching solution of zinc-cobalt solid waste, or zinc-cobalt electronic garbage leaching solution, or industrial wastewater containing zinc and cobalt. Wherein the concentration of zinc ions is 0.5 to 185g/L, such as 1g/L, 10g/L, 30g/L, 40g/L, 50g/L, 70g/L, 90g/L, 100g/L, 110g/L, 130g/L, 140g/L, 150g/L, 170g/L, 180g/L; the concentration of cobalt ions is 1mg/L to 5g/L, such as 1mg/L, 10mg/L, 100mg/L, 200mg/L, 300mg/L, 400mg/L, 500mg/L, 600mg/L, 700mg/L, 800mg/L, 900mg/L, 1g/L, 2g/L, 3g/L, 4g/L, 5g/L, for example.
Specifically, in the step 1, the problem that the too high pH of the solution causes hydrolysis and precipitation of zinc ions in the subsequent step is considered, so that the separation efficiency of zinc and cobalt ions is affected; too low a solution pH will affect the efficiency of the complexation precipitation of the precipitant with cobalt ions in subsequent steps. Therefore, the pH of the solution adjusted in step 1 is controlled to be 4.5 to 6.0.
In the step 1, the pH adjuster is an inorganic acid or base, such as sulfuric acid, hydrochloric acid, or sodium hydroxide.
Specifically, in the step 2, the excessive temperature will decompose the precipitant, resulting in unnecessary loss of the precipitant; the difficulty of temperature control in the treatment process is aggravated if the temperature is too low; thus, the temperature is controlled to be 20 to 50 ℃, for example, 20 ℃, 25 ℃, 30 ℃, 35 ℃, 40 ℃, 45 ℃,50 ℃.
Specifically, in the step 2, the cobalt ion chelating precipitant is one or a mixture of sodium ethyl xanthate and potassium ethyl xanthate.
Considering that the addition amount of the cobalt ion chelating precipitant is too low, the removal rate of cobalt ions in the solution is low; the excessive addition of the precipitant can cause reagent waste and solution pollution. Thus, in step 2 above, the molar ratio of the added amount of the cobalt ion chelating precipitant to the cobalt ions in the solution is controlled to be 4:1 to 10:1, for example, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, 10:1.
Specifically, in the step 2, the particle stabilizer includes anhydrous copper sulfate and/or hydrous copper sulfate.
Specifically, in the step 2, the principle of stabilizing the cobalt ion chelating precipitation product by the copper sulfate is as follows: copper sulfate can be used as an oxidant in the cobalt removal process to remove Co in solution 2+ Oxidation to Co 3+ In Co 3+ Cu is combined with cobalt ion chelating precipitant to form flocculent precipitate + And also combined with the cobalt ion chelating precipitant to form flocculent precipitate, which promotes the enlargement and stable existence of cobalt-containing flocculent precipitate particles. Taking sodium ethyl xanthate as an example:
8C 2 H 5 OCS 2 Na+2CuSO 4 +2CoSO 4 ＝Cu 2 (C 2 H 5 OCS 2 )↓+2Co(C 2 H 5 OCS 2 ) 3 ↓+4Na 2 SO 4
considering that the addition amount of the particle stabilizer is too low, the removal rate of cobalt ions in the solution is low; the excessive addition of the particle stabilizer can cause reagent waste and copper ion pollution to the solution. Thus, the molar ratio of the added amount of the particle stabilizer to cobalt ions in the solution is controlled to be 1:1 to 3:1, for example, 1:1, 1.5:1, 2:1, 2.5:1, 3:1.
Specifically, in the step 2, the particles are difficult to aggregate and grow up due to the too high stirring speed, and the subsequent flotation is adversely affected; too short stirring time can cause insufficient chelating precipitation; too long time affects the processing efficiency. Thus, the stirring rate is controlled to be less than or equal to 100rpm for a stirring time of 10 to 60 minutes, for example, 10 minutes, 15 minutes, 20 minutes, 25 minutes, 30 minutes, 35 minutes, 40 minutes, 45 minutes, 50 minutes, 55 minutes, 60 minutes.
Specifically, in the step 3, the surfactant is one or more of Cetyl Trimethyl Ammonium Bromide (CTAB), sodium Dodecyl Sulfate (SDS) and methyl isobutyl carbinol (MIBC).
Specifically, in the step 3, the surfactant is used for further controlling the particle size and stability. Considering that excessive addition of surfactant can cause surfactant residue in the solution; too small an amount of the additive does not play a role in regulating the particle size. Thus, the amount of the surfactant to be added is controlled to be 10 to 100mg/L, for example, 10mg/L, 15mg/L, 20mg/L, 25mg/L, 30mg/L, 40mg/L, 45mg/L, 50mg/L, 55mg/L, 60mg/L, 65mg/L, 70mg/L, 75mg/L, 80mg/L, 85mg/L, 90mg/L, 95mg/L, 100mg/L.
Specifically, in the step 3, the stirring and mixing time is 5-60 min, for example, 5min, 10min, 15min, 20min, 25min, 30min, 35min, 40min, 45min, 50min, 55min, and 60min.
Specifically, in the step 3, factors influencing the particle size of the suspended particles mainly include the addition amount of the particle stabilizer, the stirring and mixing time, the stirring speed, the ion concentration and the like; considering that the particle size of suspended particles is too small, the suspended particles are difficult to adhere to bubbles in the flotation process and then are separated in a flotation mode; the particle size is too large, the mass is large, and the momentum is high, so that the particles are difficult to carry out by bubbles. Therefore, the above parameters are strictly controlled to ensure that the particle diameter of the suspended particles is 20 to 50. Mu.m.
It should be noted that, through intensive studies, the inventors found that, due to the low concentration of cobalt ions in the solution, the particles formed are smaller, if a precipitation filtration method is adopted, the filter cloth is easily blocked, if a precipitation filtration method is adopted, large particle precipitation is required to be formed, the production time is long, and more excessive reaction reagent is required to enlarge the particles; the production efficiency is low, the consumption of the reaction reagent is large, and the economical efficiency is poor; thus, in step 4, the second intermediate system is subjected to aerated flotation using a flotation separation device.
Specifically, in the step 4, the flotation separation apparatus includes a flotation machine or a flotation column.
Specifically, in the step 4, the step of air flotation includes: introducing the second intermediate system into a flotation separation device, and performing air flotation; the particles containing cobalt precipitate float up with the bubbles and are concentrated in the upper froth layer, being collected as the froth is discharged.
Or in the steps 1-4, introducing the solution containing zinc and cobalt ions into a flotation separation device, and then adjusting the pH of the solution containing zinc and cobalt ions to be acidic; and then proceeds to step 2-4.
Compared with the prior art, the existing method for separating zinc and cobalt in the solution generally adopts a precipitation method, however, under some conditions, the cobalt ion concentration is lower, larger precipitation particles are difficult to form, and the dosage of the precipitant is required to be increased so as to ensure that the formed precipitation particles meet the requirement of filtering separation on the particle size. Long production times and more excess reagent is required to enlarge the particles; the production efficiency is low, the consumption of the reactant is large, and the economical efficiency is poor. According to the technical scheme, the cobalt ion chelating precipitant is utilized to selectively chelate cobalt ions in the solution, and the cobalt ions and the cobalt ion chelating precipitant form suspended precipitation particles through the particle stabilizing agent added simultaneously, so that the flotation separation of small cobalt ion chelating precipitation particles in the solution is realized by adopting a microbubble flotation technology, and finally, the selective extraction of low-concentration cobalt ions in the solution is realized, so that the purpose of efficiently separating zinc ions and cobalt ions in the solution is achieved; the method has the advantages of less reagent consumption, short reaction time, high production efficiency, obvious economic benefit and good zinc-cobalt separation effect.
Example 1
The embodiment provides a method for separating zinc and cobalt ions in a solution, which comprises the following steps:
adding a pH regulator into a solution containing 0.5g/L zinc ions and 1mg/L cobalt ions, and regulating the pH value of the solution to be 4.5; controlling the temperature of the solution to be 20 ℃, adding a cobalt ion chelating precipitant (100% sodium ethyl xanthate) into the solution, wherein the molar ratio of the addition to cobalt ions in the solution is 4:1, and simultaneously adding a particle stabilizer (anhydrous copper sulfate), and the molar ratio of the addition to cobalt ions in the solution is 1:1; stirring for 10min at a stirring speed of 50rpm to obtain a solution (a first intermediate system) containing cobalt ion chelate precipitate particles; then adding 10mg/L cetyltrimethylammonium bromide (CTAB) as a surfactant into the first intermediate system, and further stirring uniformly to obtain a cobalt precipitation suspension (second intermediate system), wherein the stirring time is 5min; and bubbling air bubbles to carry out floatation, and drying the floated foam product to obtain the cobalt-rich substance. Through the chelating precipitation-floatation process, 95.7% of cobalt ions in the solution can be recovered through floatation, the recovery rate of zinc ion floatation is 1.1%, the zinc ion content in the obtained cobalt-rich substance is 3.5%, and the zinc-cobalt separation effect is good.
Example 2
The embodiment provides a method for separating zinc and cobalt ions in a solution, which comprises the following steps:
adding a pH regulator into a solution containing 75g/L zinc ions and 1g/L cobalt ions, and regulating the pH value of the solution to be 5.5; controlling the temperature of the solution to be 40 ℃, adding a cobalt ion chelating precipitant (100% potassium ethylxanthate) into the solution, wherein the molar ratio of the addition to the cobalt ions in the solution is 7:1, and simultaneously adding a particle stabilizer (anhydrous copper sulfate), and the molar ratio of the addition to the cobalt ions in the solution is 2:1; stirring for 30min at a stirring speed of 75rpm to obtain a solution (a first intermediate system) containing cobalt ion chelate precipitate particles; then adding 50mg/L cetyltrimethylammonium bromide (CTAB) as a surfactant into the mixed solution, and further stirring uniformly to obtain a cobalt precipitation suspension (second intermediate), wherein the stirring time is 30min; and bubbling air bubbles to carry out floatation, and drying the floated foam product to obtain the cobalt-rich substance. Through the chelating precipitation-floatation process, 97.8% of cobalt ions in the solution can be recovered through floatation, the recovery rate of zinc ion floatation is 1.5%, the zinc ion content in the obtained cobalt-rich substance is 4.7%, and the zinc-cobalt separation effect is good.
Example 3
The embodiment provides a method for separating zinc and cobalt ions in a solution, which comprises the following steps:
adding a pH regulator into a solution containing 185g/L zinc ions and 5g/L cobalt ions, and regulating the pH value of the solution to be 6.0; controlling the temperature of the solution to be 50 ℃, adding a cobalt ion chelating precipitant (50% sodium ethyl xanthate and 50% potassium ethyl xanthate) into the solution, wherein the molar ratio of the addition of the precipitant to cobalt ions in the solution is 10:1, and simultaneously adding a particle stabilizer (copper sulfate pentahydrate), and the molar ratio of the addition of the precipitant to cobalt ions in the solution is 3:1; stirring for 60min at a stirring speed of 100rpm to obtain a solution (a first intermediate system) containing cobalt ion chelate precipitate particles; then adding 100mg/L cetyltrimethylammonium bromide (CTAB) as a surfactant into the mixed solution, and further stirring uniformly to obtain a cobalt precipitation suspension (second intermediate), wherein the stirring time is 60min; and bubbling air bubbles to carry out floatation, and drying the floated foam product to obtain the cobalt-rich substance. Through the chelating precipitation-floatation process, 94.2% of cobalt ions in the solution can be recovered through floatation, the recovery rate of zinc ion floatation is 1.4%, the zinc ion content in the obtained cobalt-rich substance is 4.8%, and the zinc-cobalt separation effect is good.
Comparative example 1
This comparative example provides a method for separating zinc and cobalt ions from a solution, which adopts a xanthate direct precipitation method to treat the same solution containing zinc and cobalt ions as in example 1. The molar ratio of the addition of the chemical reagent to the cobalt ions in the solution is 13:1, a step of; the time of the precipitation treatment is 3-5h; the cobalt ion precipitation of 87.5% in the solution can be recovered, the zinc ion precipitation rate is 8.5%, and the zinc ion content in the obtained cobalt-rich substance is 10.8%. The comparative example has long reaction time, low efficiency, low cobalt recovery rate and poor zinc-cobalt separation effect.
According to the technical scheme, the cobalt ion chelating precipitant is utilized to selectively chelate cobalt ions in the solution, and the cobalt ions and the cobalt ion chelating precipitant form suspended precipitation particles through the particle stabilizing agent added simultaneously, so that the flotation separation of small cobalt ion chelating precipitation particles in the solution is realized by adopting a flotation technology, and finally, the selective extraction of low-concentration cobalt ions in the solution is realized, so that the purpose of efficiently separating zinc ions and cobalt ions in the solution is achieved. The method has the advantages of less reagent consumption, short reaction time, high production efficiency, obvious economic benefit and good zinc-cobalt separation effect.
The present invention is not limited to the above-mentioned embodiments, and any changes or substitutions that can be easily understood by those skilled in the art within the technical scope of the present invention are intended to be included in the scope of the present invention.

Claims (7)

1. A method for separating zinc and low-concentration cobalt ions in a solution, which is characterized by comprising the following steps:
step 1, adjusting the pH value of a solution containing zinc and cobalt ions to 4.5 through a pH regulator; in the step 1, in the solution containing zinc and cobalt ions, the concentration of the zinc ions is 0.5-185 g/L, and the concentration of the cobalt ions is 1mg/L; the pH regulator is inorganic acid or alkali; the pH is adjusted to 4.5 to avoid zinc ion hydrolysis and precipitation in the subsequent step, and the separation efficiency of zinc and cobalt ions is improved;
step 2, simultaneously adding a cobalt ion chelating precipitant and a particle stabilizer into the solution at a certain temperature, and stirring and mixing to obtain a first intermediate system; the first intermediate system is a solution containing cobalt ion chelating suspended precipitation particles; the molar ratio of the addition of the cobalt ion chelating precipitant to cobalt ions in the solution is 4:1-9:1; the molar ratio of the addition of the particle stabilizer to cobalt ions in the solution is 1:1; the temperature is 20-30 ℃;
step 3, adding a surfactant into the first intermediate system, and stirring and uniformly mixing to obtain a second intermediate system; the second intermediate system is a suspension containing cobalt precipitation suspended particles; wherein, the surfactant is used for further regulating and controlling the particle size and the stability;
step 4, carrying out aerated flotation on the second intermediate system by adopting a flotation separation device, and collecting particles containing cobalt precipitates;
in the step 3, the surfactant is cetyl trimethyl ammonium bromide, and the addition amount of the surfactant is 10-15 mg/L; stirring and mixing for 5-60 min;
in the step 3, the particle diameter of the suspended particles is 20-50 μm.
2. The method for separating zinc and low-concentration cobalt ions from a solution according to claim 1, wherein in the step 1, the concentration of zinc ions in the solution containing zinc and cobalt ions is 1-185 g/L.
3. The method for separating zinc and cobalt ions having a low concentration in a solution according to claim 1, wherein in the step 2, the temperature is 20 to 25 ℃.
4. The method for separating zinc and low-concentration cobalt ions in solution according to claim 1, wherein in the step 2, the cobalt ion chelating precipitant is one or a mixture of sodium ethyl xanthate and potassium ethyl xanthate.
5. The method for separating zinc and low-concentration cobalt ions in solution according to claim 1, wherein in the step 2, the molar ratio of the addition amount of the cobalt ion chelating precipitant to the cobalt ions in solution is 4:1-8:1.
6. The method for separating zinc and low concentration cobalt ions in solution according to claim 1, wherein in the step 2, the particle stabilizer comprises anhydrous copper sulfate and/or hydrous copper sulfate.
7. The method for separating zinc and low-concentration cobalt ions in solution according to claim 1, wherein in the step 2, the stirring speed is less than or equal to 100rpm, and the stirring time is 10-55 min.
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GB278851A (en) * 1926-09-01 1927-10-20 Royale Hillman Stevens Improvements in the purification of zinc solutions preparatory to recovery of zinc by electrolysis
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