CN113957248A - Zinc-cobalt separation method for selective precipitation flotation of cobalt ions in acid solution - Google Patents
Zinc-cobalt separation method for selective precipitation flotation of cobalt ions in acid solution Download PDFInfo
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- 229910001429 cobalt ion Inorganic materials 0.000 title claims abstract description 119
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 title claims abstract description 119
- 238000005188 flotation Methods 0.000 title claims abstract description 55
- 238000000926 separation method Methods 0.000 title claims abstract description 53
- 238000001556 precipitation Methods 0.000 title claims abstract description 33
- HSSJULAPNNGXFW-UHFFFAOYSA-N [Co].[Zn] Chemical compound [Co].[Zn] HSSJULAPNNGXFW-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 239000002253 acid Substances 0.000 title abstract description 11
- 239000002245 particle Substances 0.000 claims abstract description 66
- 239000010941 cobalt Substances 0.000 claims abstract description 59
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 59
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 59
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 47
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 39
- 239000011701 zinc Substances 0.000 claims abstract description 39
- 238000000034 method Methods 0.000 claims abstract description 36
- 238000003756 stirring Methods 0.000 claims abstract description 31
- 239000012716 precipitator Substances 0.000 claims abstract description 22
- 239000003381 stabilizer Substances 0.000 claims abstract description 20
- 239000002244 precipitate Substances 0.000 claims abstract description 19
- 239000004094 surface-active agent Substances 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 239000000243 solution Substances 0.000 claims description 102
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 17
- YXAOOTNFFAQIPZ-UHFFFAOYSA-N 1-nitrosonaphthalen-2-ol Chemical group C1=CC=CC2=C(N=O)C(O)=CC=C21 YXAOOTNFFAQIPZ-UHFFFAOYSA-N 0.000 claims description 9
- 239000003929 acidic solution Substances 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 3
- 150000007522 mineralic acids Chemical group 0.000 claims description 3
- 239000003002 pH adjusting agent Substances 0.000 claims description 3
- 230000000694 effects Effects 0.000 description 11
- 239000003153 chemical reaction reagent Substances 0.000 description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 10
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 8
- 230000008901 benefit Effects 0.000 description 8
- 238000000605 extraction Methods 0.000 description 8
- 239000000126 substance Substances 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000002386 leaching Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- ZOOODBUHSVUZEM-UHFFFAOYSA-N ethoxymethanedithioic acid Chemical compound CCOC(S)=S ZOOODBUHSVUZEM-UHFFFAOYSA-N 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000011084 recovery Methods 0.000 description 5
- 239000012991 xanthate Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000007664 blowing Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000006260 foam Substances 0.000 description 3
- 239000010842 industrial wastewater Substances 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 3
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 3
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 239000002893 slag Substances 0.000 description 3
- WVYWICLMDOOCFB-UHFFFAOYSA-N 4-methyl-2-pentanol Chemical compound CC(C)CC(C)O WVYWICLMDOOCFB-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 2
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 230000009920 chelation Effects 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 239000002910 solid waste Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910000074 antimony hydride Inorganic materials 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000011549 displacement method Methods 0.000 description 1
- 239000010793 electronic waste Substances 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000009854 hydrometallurgy Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- -1 iron ion Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 239000010926 waste battery Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
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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
-
- 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
- C22B19/00—Obtaining zinc or zinc oxide
- C22B19/20—Obtaining zinc otherwise than by distilling
-
- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- 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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- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a zinc-cobalt separation method for selective precipitation flotation of cobalt ions in an acid solution, belongs to the technical field of element separation, and solves the problems of low cobalt ion separation efficiency and incomplete cobalt ion separation 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 containing cobalt ion chelating precipitation particles; step 3, adding a surfactant into the first intermediate system, and uniformly stirring and mixing to obtain a second intermediate system containing cobalt precipitate suspended 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
Technical Field
The invention belongs to the technical field of element separation, and particularly relates to a zinc-cobalt separation method for selective precipitation flotation of cobalt ions in an acid solution.
Background
Cobalt is a strategic key metal supporting the development of the high-tech field. With the popularization of electronic products and the popularization of new energy automobiles, cobalt is more and more widely applied to battery materials, and the demand of cobalt is increasing day by day. At present, China becomes the first major country for cobalt consumption. However, the cobalt reserves in China only account for 1.1 percent of the global reserves, the external dependence degree exceeds 90 percent, and most of the cobalt reserves are associated with sulfide ores of metals such as zinc, copper, nickel and the like. The cobalt grade of the cobalt-containing mineral is generally low, the direct smelting extraction process is difficult, the cost is high, and the yield of the cobalt-containing mineral cannot meet the rapidly-increased cobalt consumption requirement of China. Therefore, the development of various secondary resources (cobalt-containing solid waste, industrial wastewater and the like) containing cobalt is an effective way for guaranteeing the supply of cobalt raw materials in China.
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. 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 both need to face the problem of high-efficiency separation of zinc and cobalt ions in the solution.
At present, zinc powder displacement method, extraction method, precipitation method and the like are mainly used as separation methods of zinc and cobalt in an acid solution. The zinc powder replacement method is to replace and reduce cobalt ions in the solution by using zinc powder and form a precipitate by using the potential difference of zinc and cobalt; however, the method needs to add zinc powder more than ten times of the theoretical number, the formed cobalt removal slag contains a large amount of unreacted zinc powder, and the extraction of cobalt in the cobalt removal slag faces the problem of zinc-cobalt separation again, so that the problem of difficult zinc-cobalt separation is not thoroughly solved. 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 fundamental reason of the difficult problem of separating the zinc and the cobalt in the solution is that the concentration of cobalt ions is generally low, and when the method is adopted for separating the zinc and the cobalt, the problems of poor selectivity, slow mass transfer process, low separation efficiency, incompleteness and the like exist. Therefore, how to separate the zinc and cobalt ions efficiently becomes an urgent problem to be solved.
Disclosure of Invention
In view of the above analysis, the present invention aims to provide a zinc-cobalt separation method for selective precipitation flotation of cobalt ions in an acidic 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 the present invention can realize high-efficiency separation of zinc and cobalt ions in the solution.
The purpose of the invention is mainly realized by the following technical scheme:
the invention provides a zinc-cobalt separation method for selective precipitation flotation of cobalt ions in an acid 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 containing cobalt ion chelating precipitation particles;
step 3, adding a surfactant into the first intermediate system, and uniformly stirring and mixing to obtain a second intermediate system containing cobalt precipitate suspended 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 2.0-3.5.
Further, in the step 1, the pH adjusting agent is an inorganic acid or an alkali.
Further, in the step 2, the cobalt ion chelating precipitator is alpha-nitroso-beta-naphthol.
Further, in the step 2, the temperature is 30-70 ℃.
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 3: 1-10: 1.
Further, in the step 2, the particle stabilizer is Fe-containing3+And (3) solution.
Further, in the step 2, the molar ratio of the addition amount of the particle stabilizer to the cobalt ions in the solution is 0.5: 1-1.5: 1.
Further, in the step 2, the stirring speed is less than or equal to 100rpm, and the stirring time is 10-60 min.
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, utilizes the selective complexation of cobalt ion chelating precipitator (alpha-nitroso-beta-naphthol) and cobalt ions, selectively chelates the cobalt ions in the solution with the cobalt ions, leads the chelate of the cobalt ions and the medicament to form stable suspended particles through the particle stabilizer added at the same time, 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 and a xanthate precipitation 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. The precipitation cobalt removal method of xanthate: 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. In order to ensure the quality of the purified solution, the excessive organic medicament in the leaching solution needs to be removed. Compared with the prior art, the method of the invention adopts a precipitation-flotation separation method to realize cobalt ion removalThe method has wide application range to the concentration of metal ions in the solution, has stronger applicability particularly 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 may be realized and attained by the instrumentalities and combinations particularly pointed out in the written description.
Detailed Description
The zinc-cobalt separation process of selective precipitation flotation of cobalt ions in an acidic solution is described in further detail below with reference to specific examples, which are provided for purposes of comparison and explanation only and to which the present invention is not limited.
A zinc-cobalt separation method for selective precipitation flotation of cobalt ions in an acidic 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 containing cobalt ion chelating precipitation particles;
step 3, adding a surfactant into the first intermediate system, and uniformly stirring and mixing to obtain a second intermediate system containing cobalt precipitate suspended 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 the step 1, the solution containing zinc and cobalt ions can be a zinc hydrometallurgy acid leaching solution, a zinc and cobalt-containing solid residue acid leaching solution, a zinc and cobalt-containing electronic waste acid leaching solution and zinc and cobalt-containing industrial wastewater, and the concentration ranges of zinc and cobalt ions are 0.5-185 g/L and 1 mg/L-5 g/L respectively. Wherein the concentration of zinc ions is 0.5-185 g/L, illustratively, such as 0.5g/L, 5g/L, 10g/L, 30g/L, 40g/L, 50g/L, 70g/L, 90g/L, 100g/L, 120g/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 chelating precipitator and cobalt ions in the subsequent steps. Therefore, the pH of the solution adjusted in step 1 is controlled to be 2.0-3.5, such as 2.0, 2.2, 2.5, 2.8, 3.0, 3.3, 3.5.
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 chelating precipitant is decomposed due to an excessively high temperature, so that unnecessary loss of the chelating precipitant is caused; if the temperature is too low, the difficulty of temperature control in the treatment process is increased; thus, the temperature is controlled to be 30-70 deg.C, illustratively 30 deg.C, 35 deg.C, 40 deg.C, 45 deg.C, 50 deg.C, 55 deg.C, 60 deg.C, 65 deg.C, 70 deg.C.
Specifically, in the step 2, the cobalt ion chelating precipitant is alpha-nitroso-beta-naphthol.
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 amount of the cobalt ion chelating precipitant to the cobalt ions in the solution is controlled to be 3:1 to 10:1, such as 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, and 10: 1.
Specifically, in the step 2, the particle stabilizer is Fe-containing3+The solution can be ferric sulfate solution and/or ferric chloride solution.
Specifically, in the step 2, Fe is contained3+Solution stable cobalt ion chelateThe principle of the synthetic precipitation product is: in view of the characteristic of low concentration of cobalt ions in the solution, in order to ensure that the size of cobalt ion chelated precipitation particles meets the requirement of the flotation process, Fe is utilized3+Susceptible to hydrolysis to form Fe (OH)3The characteristic of floc precipitation realizes the regulation and control of the particle size of cobalt ion chelation precipitation, so that finer precipitation particles grow into particles meeting the flotation requirement.
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 iron ion contamination of the solution. Thus, the molar ratio of the added amount of the particle stabilizer to the cobalt ions in the solution is controlled to be 0.5:1 to 1.5:1, illustratively, 0.5:1, 0.7:1, 0.8:1, 1:1, 1.2:1, 1.3:1, 1.5: 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, 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 particle diameter of the suspended particles is controlled to be 20 to 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 alpha-nitroso-beta-naphthol is selectively chelated with cobalt ions in the solution, the cobalt ions and the cobalt ion chelating precipitator form stable suspended precipitated particles through the particle stabilizer added at the same time, then the flotation separation of the cobalt ion chelating precipitated particles in the solution is realized by adopting 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 zinc-cobalt separation method for selective precipitation flotation of cobalt ions in an acid 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 2.0; controlling the temperature of the solution at 30 ℃, adding a cobalt ion chelating precipitator (alpha-nitroso-beta-naphthol) 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 3:1, and simultaneously adding a particle stabilizer (ferric sulfate solution), wherein the molar ratio of the added amount of the iron chelating precipitator to the cobalt ions in the solution is 0.5: 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 mixed solution, and further uniformly stirring to obtain a second intermediate system containing cobalt precipitate suspended particles, 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, 85.1 percent of cobalt ions in the solution can be recovered by flotation, the zinc ion flotation recovery rate is 2.1 percent, the zinc ion content in the obtained cobalt-rich substance is 2.1 percent, and the zinc-cobalt separation effect is good.
Example 2
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 2.5; controlling the temperature of the solution to be 45 ℃, adding a cobalt ion chelating precipitator (alpha-nitroso-beta-naphthol) 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 5:1, and simultaneously adding a particle stabilizer (ferric chloride solution), wherein the molar ratio of the added amount of the iron chelating precipitator to the cobalt ions in the solution is 1: 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 second intermediate system containing cobalt precipitate suspended particles, 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, 90.8 percent of cobalt ions in the solution can be recovered by flotation, the zinc ion flotation recovery rate is 1.3 percent, the zinc ion content in the obtained cobalt-rich substance is 3.6 percent, and the zinc-cobalt separation effect is good.
Example 3
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 3.5; controlling the temperature of the solution at 70 ℃, adding a cobalt ion chelating precipitator (alpha-nitroso-beta-naphthol) 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 10:1, and simultaneously adding a particle stabilizer (a mixed solution of ferric sulfate and ferric chloride), wherein the molar ratio of the added amount of the particle stabilizer to the cobalt ions in the solution is 1.5: 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 second intermediate system containing cobalt precipitate suspended particles, 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, 97.3 percent of cobalt ions in the solution can be recovered by flotation, the zinc ion flotation recovery rate is 1.6 percent, the zinc ion content in the obtained cobalt-rich substance is 3.9 percent, and the zinc-cobalt separation effect is good.
Comparative example 1
This comparative example provides a method for separating zinc and cobalt ions by direct precipitation with xanthate, the same solution containing zinc and cobalt ions as in example 1 was treated. 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, cobalt ion chelating precipitator (alpha-nitroso-beta-naphthol) is selectively chelated with cobalt ions in the solution, the cobalt ions and the cobalt ion chelating precipitator form stable suspended precipitate particles through the particle stabilizer added at the same time, then the flotation separation of the 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 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 zinc-cobalt separation method for selective precipitation flotation of cobalt ions in an acidic 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 containing cobalt ion chelating precipitation particles;
step 3, adding a surfactant into the first intermediate system, and uniformly stirring and mixing to obtain a second intermediate system containing cobalt precipitate suspended 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 according to claim 1, wherein in the solution containing zinc and cobalt ions in step 1, the concentration of zinc 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 according to claim 1, wherein the pH of the solution after adjustment in step 1 is 2.0 to 3.5.
4. The method of claim 1, wherein in step 1, the pH adjusting agent is an inorganic acid or an alkali.
5. The method for separating zinc and cobalt as claimed in claim 1, wherein in step 2, the cobalt ion chelating precipitant is α -nitroso- β -naphthol.
6. The zinc-cobalt separation method according to claim 1, wherein the temperature in step 2 is 30 to 70 ℃.
7. The zinc-cobalt separation method 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 3: 1-10: 1.
8. The method of claim 1, wherein in step 2, the particle stabilizer is Fe-containing3 +And (3) solution.
9. The zinc-cobalt separation method 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 0.5: 1-1.5: 1.
10. The zinc-cobalt separation method according to claims 1 to 9, wherein in the step 2, the stirring speed is less than or equal to 100rpm, and the stirring time is 10-60 min.
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