CN113957249A - Method for separating zinc and cobalt ions in solution - Google Patents

Method for separating zinc and cobalt ions in solution Download PDF

Info

Publication number
CN113957249A
CN113957249A CN202110064638.1A CN202110064638A CN113957249A CN 113957249 A CN113957249 A CN 113957249A CN 202110064638 A CN202110064638 A CN 202110064638A CN 113957249 A CN113957249 A CN 113957249A
Authority
CN
China
Prior art keywords
cobalt
solution
zinc
cobalt ions
ions
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN202110064638.1A
Other languages
Chinese (zh)
Other versions
CN113957249B (en
Inventor
黄宇坤
曹亦俊
范桂侠
彭伟军
白宁宁
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Zhengzhou University
Original Assignee
Zhengzhou University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Zhengzhou University filed Critical Zhengzhou University
Priority to CN202110064638.1A priority Critical patent/CN113957249B/en
Publication of CN113957249A publication Critical patent/CN113957249A/en
Application granted granted Critical
Publication of CN113957249B publication Critical patent/CN113957249B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Manufacture And Refinement Of Metals (AREA)

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 separation efficiency and incomplete separation of the zinc and cobalt ions in the prior art. The method comprises the following steps: step 1, adjusting the pH of a solution containing zinc and cobalt ions to acidity by a pH regulator; step 2, simultaneously adding a cobalt ion chelating precipitator 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 chelated precipitated particles; step 3, adding a surfactant into the first intermediate system, and uniformly stirring and mixing to obtain a second intermediate system; the second intermediate system is a suspension containing cobalt precipitate suspension particles; and 4, performing air flotation on the second intermediate system by adopting a flotation separation device, and collecting particles containing cobalt precipitates. The method of the invention effectively solves the difficult problem of separating zinc and cobalt.

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 ions and cobalt ions in a solution.
Background
Cobalt is a strategic metal resource supporting the development of the high-tech field. Along with the popularization of electronic products and the popularization of new energy automobiles, the application of cobalt in battery materials is more and more extensive, and the demand of cobalt is increased day by day. However, the global cobalt reserves are only around 700 million tons, and the distribution is relatively concentrated. The reserves of China only account for 1.1 percent of the reserves of China, and most of the reserves are associated with sulfide ores of metals such as zinc, copper, nickel and the like, and the direct smelting and extraction of the cobalt-containing minerals have the disadvantages of high process difficulty and high cost and are difficult to meet the rapidly-increasing cobalt consumption demands of China. Therefore, the 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 ensuring the supply of cobalt raw materials.
The smelting slag containing zinc and cobalt, industrial solid wastes and waste battery materials are important secondary resources containing cobalt, and metal components can enter a leaching solution through an acid leaching process; in addition, some industrial wastewater contains zinc and cobalt ions at a certain concentration. Both the separation and extraction of cobalt in the secondary resource containing zinc and cobalt and the purification and impurity removal of cobalt in the solution need 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 needed.
At present, zinc and cobalt in solution are separated mainly by zinc powder displacement method, extraction method, precipitation method, etc. 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 more than ten times of the theoretical amount of zinc powder, and the formed cobalt removal slag contains a large amount of unreacted zinc powder, so that the extraction of cobalt in the cobalt removal slag faces the problem of zinc-cobalt separation again. When the solvent extraction method is adopted to separate the zinc and the cobalt in the solution, the extraction effect is poor because the cobalt ion content in the solution is generally low; meanwhile, when the precipitation method is adopted to separate the zinc and the cobalt in the solution, the precipitant can comprise sulfide, xanthate and the like, but is also influenced by low cobalt ion content, larger precipitated particles are difficult to form, the precipitation process is slow, and the complete separation is difficult.
The method for separating the 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 the cobalt ions in the solution. Therefore, how to separate the zinc and cobalt ions in the solution efficiently becomes an urgent problem to be solved.
Disclosure of Invention
In view of the above analysis, the present invention aims to provide a method for separating zinc and cobalt ions from a solution, so as to solve the problems of poor selectivity, low separation efficiency and incomplete separation caused by low cobalt ion concentration in the solution in the prior art, and to achieve efficient separation of zinc and cobalt ions from the solution.
The purpose 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 of a solution containing zinc and cobalt ions to acidity by a pH regulator;
step 2, simultaneously adding a cobalt ion chelating precipitator 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 chelated precipitated particles;
step 3, adding a surfactant into the first intermediate system, and uniformly stirring and mixing to obtain a second intermediate system; the second intermediate system is a suspension containing cobalt precipitate suspension particles;
and 4, performing air flotation on the second intermediate system by adopting a flotation separation device, and collecting particles containing cobalt precipitates.
Further, 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 1 mg/L-5 g/L.
Further, in the step 1, the pH value of the adjusted solution is 4.5-6.0.
Further, in the step 2, the temperature is 20-50 ℃.
Further, in the step 2, the cobalt ion chelating precipitator 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 precipitator to the cobalt ions in the solution is 4: 1-10: 1.
Further, in the step 2, the particle stabilizer comprises 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 the cobalt ions in the solution is 1: 1-3: 1.
Further, in the 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 20-50 μm.
Compared with the prior art, the invention can at least realize one of the following technical effects:
1) the invention firstly applies the chelating precipitation-flotation method to the separation of zinc and cobalt ions in the solution, selectively chelates the cobalt ions in the solution by utilizing the selective complexation of the cobalt ion chelating precipitator, leads the chelate of the cobalt ions and the medicament to form suspended particles by simultaneously adding the particle stabilizer, and finally realizes the selective extraction of the cobalt ions in the solution by the micro-bubble flotation technology, thereby achieving the purpose of efficiently separating the zinc and the cobalt ions in the solution. The method can be used for separating the zinc ions and the cobalt ions in various solutions containing the low-concentration cobalt ions and removing the cobalt ions, and has the advantages of good zinc-cobalt separation effect, high cobalt ion recovery rate, low cost and short process.
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 replacement method: the zinc powder consumption is large, generally more than 20 times of theoretical quantity, the operation time is long, the operation is required to be carried out at about 80 ℃, and AsH is often generated3And SbH3A toxic gas. Removing cobalt from xanthateThe method comprises the following steps: because the concentration of cobalt ions in the solution is low, excessive xanthate must be added for the reaction to be rapidly carried out and the cobalt removal is thorough, and the dosage is generally 10-15 times of the theoretical dosage. The cobalt removal method of alpha-nitroso-beta-naphthol: the method has the same defects as the method for removing cobalt by using xanthate, the dosage of the medicament is large, and in order to ensure the electrolytic quality of the purified liquid, the excessive organic medicament in the leaching solution needs to be adsorbed by adopting activated carbon. Compared with the existing method, the method has the advantages that the method has wide application range on the concentration of metal ions in the solution, particularly has stronger applicability in the aspect of removing 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 the 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, wherein like reference numerals are used to designate like parts throughout.
FIG. 1 is a process flow diagram of the separation process of the present invention.
Detailed Description
The following is a more detailed description of the method for separating zinc and cobalt ions from a solution, taken in conjunction with specific examples, which are provided for purposes of comparison and explanation only and to which the present invention is not limited.
A method for separating zinc and cobalt ions in a solution comprises the following steps:
step 1, adjusting the pH of a solution containing zinc and cobalt ions to acidity by a pH regulator;
step 2, simultaneously adding a cobalt ion chelating precipitator and a particle stabilizer into the solution at a certain temperature, and stirring and mixing to obtain a first intermediate system; the first intermediate is a solution containing cobalt ion chelated precipitate particles;
step 3, adding a surfactant into the first intermediate system, and uniformly stirring and mixing to obtain a second intermediate system; the second intermediate system is a suspension containing cobalt precipitate suspension particles;
and 4, performing air flotation on the second intermediate system by adopting a flotation separation device, collecting particles containing cobalt precipitates, realizing selective chelation precipitation-flotation removal of cobalt ions in the solution, and realizing high-efficiency separation of zinc and cobalt.
Specifically, in step 1, the solution containing zinc and cobalt ions may be a zinc hydrometallurgy leachate, or an acid leachate of a solid waste containing zinc and cobalt, or an electronic garbage leachate containing zinc and cobalt, or an industrial wastewater containing zinc and cobalt. Wherein the concentration of zinc ions is 0.5-185 g/L, illustratively, 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, 180 g/L; the concentration of cobalt ions is 1mg/L to 5g/L, illustratively, 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, 5 g/L.
Specifically, in the step 1, it is considered that the excessive pH of the solution causes hydrolysis and precipitation of zinc ions in subsequent steps, thereby affecting the separation efficiency of zinc and cobalt ions; the pH value of the solution is too low, which influences the complexing precipitation efficiency of the precipitant and cobalt ions in the subsequent steps. Therefore, the pH of the solution adjusted in the step 1 is controlled to be 4.5-6.0.
In step 1, the pH adjuster is an inorganic acid or an alkali, 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; if the temperature is too low, the difficulty of temperature control in the treatment process is increased; thus, the temperature is controlled to be 20-50 deg.C, illustratively 20 deg.C, 25 deg.C, 30 deg.C, 35 deg.C, 40 deg.C, 45 deg.C, 50 deg.C.
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 removal rate of cobalt ions in the solution is low when the addition amount of the cobalt ion chelating precipitator is too low; if the amount of the precipitant is too high, the reagent is wasted and the solution is contaminated. Therefore, in the step 2, the molar ratio of the added cobalt ion chelating precipitant to the cobalt ions in the solution is controlled to be 4: 1-10: 1, such as 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, and 10: 1.
Specifically, in 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 chelated precipitate product by copper sulfate is as follows: copper sulfate can be used as an oxidant in the cobalt removal process to remove Co in solution2+Oxidation to Co3+In Co3+Cu forms flocculent precipitate by combining with cobalt ion chelating precipitant+And also forms flocculent precipitate by combining with the cobalt ion chelating precipitator, so as to promote the enlargement and stable existence of cobalt-containing flocculent precipitate particles. Taking sodium ethyl xanthate as an example:
8C2H5OCS2Na+2CuSO4+2CoSO4＝Cu2(C2H5OCS2)↓+2Co(C2H5OCS2)3↓+4Na2SO4
considering that the removal rate of cobalt ions in the solution is low when the addition amount of the particle stabilizer is too low; too high an amount of particulate stabilizer added results in waste of reagents and contamination of the solution with copper ions. Therefore, the molar ratio of the added amount of the particle stabilizer to the cobalt ions in the solution is controlled to be 1:1 to 3:1, such as 1:1, 1.5:1, 2:1, 2.5:1, and 3: 1.
Specifically, in the step 2, too high stirring speed can cause particles to be difficult to aggregate and grow up, and adverse effect is caused on subsequent flotation; insufficient chelating precipitation can be caused by too short stirring time; too long time affects the processing efficiency. Therefore, the stirring speed is controlled to be less than or equal to 100rpm, and the stirring time is 10-60 min, such as 10min, 15min, 20min, 25min, 30min, 35min, 40min, 45min, 50min, 55min, 60 min.
Specifically, in the step 3, the surfactant is one or more of cetyltrimethylammonium bromide (CTAB), Sodium Dodecyl Sulfate (SDS), and methyl isobutyl carbinol (MIBC).
Specifically, in step 3, the surfactant is used to further control the particle size and stability. Considering that the excessive addition of the surfactant can cause the residue of the surfactant in the solution; if the addition amount is too small, the effect of regulating the particle size cannot be achieved. Therefore, the amount of the surfactant added is controlled to be 10 to 100mg/L, illustratively, 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, 100 mg/L.
Specifically, in the step 3, the stirring and mixing time is 5-60 min, such as 5min, 10min, 15min, 20min, 25min, 30min, 35min, 40min, 45min, 50min, 55min, and 60 min.
Specifically, in step 3, the 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 the suspended particles is too small, the particles are difficult to adhere by bubbles in the flotation process and then are separated in a flotation mode; the particles have overlarge size, large mass and high momentum and are difficult to be brought out by bubbles. Therefore, the parameters are strictly controlled to ensure that the particle diameter of the suspended particles is 20-50 μm.
It should be noted that the inventors have intensively studied and found that, since the concentration of cobalt ions in the solution is low, the formed particles are small, the filter cloth is easily clogged if the precipitation filtration method is used, large particle precipitates need to be formed if the precipitation filtration method is used, the production time is long, and more excessive reaction reagents are required to enlarge the particles; the production efficiency is low, the consumption of reaction reagents is large, and the economical efficiency is poor; therefore, in step 4, the second intermediate system is subjected to air flotation by using a flotation separation device.
Specifically, in step 4, the flotation separation device 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 precipitates float up with the bubbles and are concentrated in the upper froth layer and are collected as the froth is discharged.
Or in the step 1-4, introducing the solution containing zinc and cobalt ions into a flotation separation device, and then adjusting the pH value of the solution containing zinc and cobalt ions to be acidic; then proceed to step 2-4.
Compared with the prior art, the existing method for separating zinc and cobalt from solution generally adopts a precipitation method, however, because the concentration of cobalt ions is lower under some conditions, larger precipitated particles are difficult to form, and the dosage of a precipitator must be increased to ensure that the formed precipitated particles meet the requirements of filtration and separation on the particle size. Long production times and more excess reagents to enlarge the particles; low production efficiency, large consumption of reaction reagents and poor economical efficiency. According to the technical scheme, the cobalt ion chelating precipitator is selectively chelated with cobalt ions in the solution, the cobalt ions and the cobalt ion chelating precipitator form suspended precipitate particles through the particle stabilizer added at the same time, then the flotation separation of small cobalt ion chelating precipitate particles in the solution is realized through a micro-bubble flotation technology, and finally the selective extraction of low-concentration cobalt ions in the solution is realized, so that the aim of efficiently separating zinc ions and cobalt ions in the solution is fulfilled; the method has the advantages of less reaction 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 ions and cobalt ions in a solution, which comprises the following steps:
adding a pH regulator into a solution containing 0.5g/L of zinc ions and 1mg/L of cobalt ions, and adjusting the pH value of the solution to 4.5; controlling the temperature of the solution at 20 ℃, adding a cobalt ion chelating precipitator (100% sodium ethyl xanthate) into the solution, wherein the molar ratio of the added cobalt ion chelating precipitator to the cobalt ions in the solution is 4:1, and simultaneously adding a particle stabilizer (anhydrous copper sulfate), wherein the molar ratio of the added cobalt ion chelating precipitator to the 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 chelated precipitate particles; then adding 10mg/L Cetyl Trimethyl Ammonium Bromide (CTAB) serving as a surfactant into the first intermediate system, and further uniformly stirring to obtain a suspension (a second intermediate system) of cobalt precipitate, wherein the stirring time is 5 min; and blowing bubbles for flotation, and drying the foam product subjected to flotation to obtain a cobalt-rich substance. Through the chelating precipitation-flotation process, 95.7 percent of cobalt ions in the solution can be recovered by flotation, the zinc ion flotation recovery rate is 1.1 percent, the zinc ion content in the obtained cobalt-rich substance is 3.5 percent, and the zinc-cobalt separation effect is good.
Example 2
The embodiment provides a method for separating zinc ions and cobalt ions in a solution, which comprises the following steps:
adding a pH regulator into a solution containing 75g/L of zinc ions and 1g/L of cobalt ions, and adjusting the pH value of the solution to 5.5; controlling the temperature of the solution at 40 ℃, adding a cobalt ion chelating precipitator (100% potassium ethyl xanthate) into the solution, wherein the molar ratio of the added amount of the cobalt ion chelating precipitator to the cobalt ions in the solution is 7:1, and simultaneously adding a particle stabilizer (anhydrous copper sulfate), wherein the molar ratio of the added amount of the particle stabilizer 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 chelated precipitate particles; then adding 50mg/L Cetyl Trimethyl Ammonium Bromide (CTAB) serving as a surfactant into the mixed solution, and further uniformly stirring to obtain a suspension (a second intermediate) of the cobalt precipitate, wherein the stirring time is 30 min; and blowing bubbles for flotation, and drying the foam product subjected to flotation to obtain a cobalt-rich substance. Through the chelating precipitation-flotation process, 97.8 percent of cobalt ions in the solution can be recovered by flotation, the zinc ion flotation recovery rate is 1.5 percent, the zinc ion content in the obtained cobalt-rich substance is 4.7 percent, and the zinc-cobalt separation effect is good.
Example 3
The embodiment provides a method for separating zinc ions and cobalt ions in a solution, which comprises the following steps:
adding a pH regulator into a solution containing 185g/L of zinc ions and 5g/L of cobalt ions, and adjusting the pH value of the solution to 6.0; controlling the temperature of the solution at 50 ℃, adding a cobalt ion chelating precipitator (50% sodium ethyl xanthate and 50% potassium ethyl xanthate) into the solution, wherein the molar ratio of the added cobalt ion chelating precipitator to the cobalt ion in the solution is 10:1, and simultaneously adding a particle stabilizer (copper sulfate pentahydrate), wherein the molar ratio of the added cobalt ion chelating precipitator to the cobalt ion 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 chelated precipitate particles; then adding 100mg/L Cetyl Trimethyl Ammonium Bromide (CTAB) serving as a surfactant into the mixed solution, and further uniformly stirring to obtain a suspension (a second intermediate) of cobalt precipitate, wherein the stirring time is 60 min; and blowing bubbles for flotation, and drying the foam product subjected to flotation to obtain a cobalt-rich substance. Through the chelating precipitation-flotation process, 94.2 percent of cobalt ions in the solution can be recovered by flotation, the zinc ion flotation recovery rate is 1.4 percent, the zinc ion content in the obtained cobalt-rich substance is 4.8 percent, 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 uses xanthate direct precipitation to treat the same solution containing zinc and cobalt ions as in example 1. The molar ratio of the added amount of the chemical reagent to the cobalt ions in the solution is 13: 1; the time of precipitation treatment is 3-5 h; 87.5 percent of cobalt ions in the solution can be precipitated and recovered, the precipitation rate of zinc ions is 8.5 percent, and the content of zinc ions in the obtained cobalt-rich substance is 10.8 percent. The comparative example has the advantages of long reaction time, low efficiency, low cobalt recovery rate and poor zinc-cobalt separation effect.
According to the technical scheme, the cobalt ion chelating precipitator is selectively chelated with cobalt ions in the solution, the cobalt ions and the cobalt ion chelating precipitator form suspended precipitated particles through the particle stabilizer added at the same time, then the flotation separation of small cobalt ion chelating precipitated particles in the solution is realized through the flotation technology, and finally the selective extraction of low-concentration cobalt ions in the solution is realized, so that the aim of efficiently separating zinc ions and cobalt ions in the solution is fulfilled. The method has the advantages of less reaction reagent consumption, short reaction time, high production efficiency, obvious economic benefit and good zinc-cobalt separation effect.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention.

Claims (10)

1. A method for separating zinc and cobalt ions in a solution is characterized by comprising the following steps:
step 1, adjusting the pH of a solution containing zinc and cobalt ions to acidity by a pH regulator;
step 2, simultaneously adding a cobalt ion chelating precipitator 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 chelated precipitated particles;
step 3, adding a surfactant into the first intermediate system, and uniformly stirring and mixing to obtain a second intermediate system; the second intermediate system is a suspension containing cobalt precipitate suspension particles;
and 4, performing air flotation on the second intermediate system by adopting a flotation separation device, and collecting particles containing cobalt precipitates.
2. The method for separating zinc and 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 0.5-185 g/L, and the concentration of cobalt ions is 1 mg/L-5 g/L.
3. The method for separating zinc and cobalt ions from a solution according to claim 1, wherein the pH of the solution after the adjustment in step 1 is 4.5 to 6.0.
4. The method for separating zinc and cobalt ions from a solution according to claim 1, wherein the temperature in step 2 is 20-50 ℃.
5. The method for separating zinc and cobalt ions from a solution according to claim 1, wherein in the step 2, the cobalt ion chelating precipitator is one or a mixture of sodium ethyl xanthate and potassium ethyl xanthate.
6. The method for separating zinc and cobalt ions from a solution according to claim 1, wherein in the step 2, the molar ratio of the added amount of the cobalt ion chelating precipitant to the cobalt ions in the solution is 4: 1-10: 1.
7. The method as claimed in claim 1, wherein the particle stabilizer in step 2 comprises anhydrous copper sulfate and/or hydrous copper sulfate.
8. The method for separating zinc and cobalt ions from a solution according to claim 1, wherein in the step 2, the molar ratio of the added amount of the particle stabilizer to the cobalt ions in the solution is 1: 1-3: 1.
9. The method for separating zinc and cobalt ions from a 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 10-60 min.
10. The method for separating zinc and cobalt ions in solution according to claims 1-9, wherein in the step 3, the particle diameter of the suspended particles is 20-50 μm.
CN202110064638.1A 2021-01-18 2021-01-18 Method for separating zinc and cobalt ions in solution Active CN113957249B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202110064638.1A CN113957249B (en) 2021-01-18 2021-01-18 Method for separating zinc and cobalt ions in solution

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202110064638.1A CN113957249B (en) 2021-01-18 2021-01-18 Method for separating zinc and cobalt ions in solution

Publications (2)

Publication Number Publication Date
CN113957249A true CN113957249A (en) 2022-01-21
CN113957249B CN113957249B (en) 2023-07-25

Family

ID=79459356

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202110064638.1A Active CN113957249B (en) 2021-01-18 2021-01-18 Method for separating zinc and cobalt ions in solution

Country Status (1)

Country Link
CN (1) CN113957249B (en)

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
CN106350673A (en) * 2016-09-30 2017-01-25 中南大学 Method for selectively precipitating and separating cobalt in potential-control manner
CN107188330A (en) * 2017-05-31 2017-09-22 郑州大学 A kind of method of adsorption cleaning acid waste water
CN109761325A (en) * 2019-02-27 2019-05-17 郑州大学 The compound adjusting control agent and method of precipitation by metallic ion conversion and flotation removing in a kind of waste water
CN109851021A (en) * 2019-02-27 2019-06-07 郑州大学 It is a kind of for strengthening the compound adjusting control agent and its application that precipitation by metallic ion floatation in waste water removes
CN110760702A (en) * 2019-11-07 2020-02-07 郑州大学 Method for selective flotation and step-by-step separation of molybdenum and rhenium in acidic solution

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
CN106350673A (en) * 2016-09-30 2017-01-25 中南大学 Method for selectively precipitating and separating cobalt in potential-control manner
CN107188330A (en) * 2017-05-31 2017-09-22 郑州大学 A kind of method of adsorption cleaning acid waste water
CN109761325A (en) * 2019-02-27 2019-05-17 郑州大学 The compound adjusting control agent and method of precipitation by metallic ion conversion and flotation removing in a kind of waste water
CN109851021A (en) * 2019-02-27 2019-06-07 郑州大学 It is a kind of for strengthening the compound adjusting control agent and its application that precipitation by metallic ion floatation in waste water removes
CN110760702A (en) * 2019-11-07 2020-02-07 郑州大学 Method for selective flotation and step-by-step separation of molybdenum and rhenium in acidic solution

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
刘永帅等: "湿法炼锌净化除钴工艺现状及发展趋势", 《矿冶》 *
容蓉等: "湿法炼锌净化除钴工艺研究现状", 《湿法冶金》 *

Also Published As

Publication number Publication date
CN113957249B (en) 2023-07-25

Similar Documents

Publication Publication Date Title
Long et al. Recovery of alkali, selenium and arsenic from antimony smelting arsenic-alkali residue
CN102994747B (en) Technology for recovering metallic copper from high-lead copper matte
CN113684368A (en) Method for co-processing arsenic sulfide slag and arsenic-containing smoke dust in copper smelting
CN103276206B (en) Method for leaching gold in alkaline thiourea system efficiently and stably
CN113549766B (en) Method for removing arsenic from lead smelting smoke dust and recovering valuable metals
CN110093506A (en) Valuable metal high efficiency extraction and its minimizing processing method in germanic zinc leaching residue
CN110512095B (en) Method for extracting and stabilizing arsenic from tungsten metallurgy phosphorus arsenic slag
CN108138258B (en) Method for removing arsenic from arsenic-containing material
CN114314661B (en) Method for producing high-purity ammonium metavanadate by deep cobalt removal of vanadium raw material
CN106179761B (en) Beneficiation method for zinc oxide ore
CN113621818A (en) Method for co-processing copper smelting waste acid and arsenic-containing smoke dust
Chen et al. Hemimorphite ores: A review of processing technologies for zinc extraction
CN111455189A (en) Method for leaching copper from tin-copper slag
GB2621039A (en) Harmless treatment method for recovering sulfur, rhenium, and arsenic from arsenic sulfide slag
CN105200242A (en) Method for revering cadmium from arsenic-containing lead-smelting oxygen bottom-blown furnace dust
CN113957248B (en) Zinc-cobalt separation method for selective precipitation flotation of cobalt ions in acidic solution
JP4529969B2 (en) Method for removing selenium from selenate-containing liquid
CN110627179A (en) Method for treating arsenic-containing wastewater by using recyclable composite salt precipitator
CN1321200C (en) Method for separating copper, arsenic and zinc from copper-smelting high-arsenic flue dust sulphuric acid leach liquor
CN111500860B (en) Process method for recovering copper from low-grade copper oxide ore
CN106565005A (en) High-sulfur floatation wastewater treatment and sodium sulfide recycling preparation method
USH1852H (en) Waste treatment of metal plating solutions
CN112358090A (en) Harmless treatment method for gold smelting cyanide-and heavy metal-containing wastewater
CN113957249B (en) Method for separating zinc and cobalt ions in solution
CN109371245B (en) Recycling treatment method for copper slag of nickel refining system

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant