CN109666800B - Cobalt removing agent and application thereof - Google Patents
Cobalt removing agent and application thereof Download PDFInfo
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- CN109666800B CN109666800B CN201910057030.9A CN201910057030A CN109666800B CN 109666800 B CN109666800 B CN 109666800B CN 201910057030 A CN201910057030 A CN 201910057030A CN 109666800 B CN109666800 B CN 109666800B
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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
- C22B7/007—Wet processes by acid leaching
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0453—Treatment or purification of solutions, e.g. obtained by leaching
- C22B23/0461—Treatment or purification of solutions, e.g. obtained by leaching by chemical methods
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
- C22B3/46—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes by substitution, e.g. by cementation
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Abstract
The invention discloses a cobalt removing agent and application thereof. The cobalt removing agent consists of dimethyl dithiocarbamate and sodium nitrite, and the mass ratio of the dimethyl dithiocarbamate is as follows: sodium nitrite 12-18: 1. The cobalt removing agent is applied to zinc smelting slag leachate for removing cobalt, the removal rate of cobalt is up to more than 99.7 percent, namely the cobalt can be approximately and completely removed, the concentration of the cobalt in the solution completely meets the requirement of zinc electrolysis, and the cobalt removing agent has extremely high selectivity, can not remove manganese ions playing a role of protection electrolysis in the solution, and in addition, in the cobalt removing process of the invention, the grade of cobalt slag obtained after heat treatment of the obtained cobalt precipitate is up to more than 58 percent, so that the cobalt removing agent has great recovery value.
Description
Technical Field
The invention relates to a cobalt removing agent and application thereof, belonging to the technical field of secondary resource recovery.
Background
Global zinc consumption is over 1300 million tons per year, and global zinc demand is expected to continue to increase in the future. However, as zinc consumption increases, the content and grade of primary zinc resources are decreasing. Meanwhile, the discharge and accumulation of a large amount of smelting waste slag cause serious resource waste and outstanding environmental problems. Therefore, from the aspects of resource utilization and environmental protection, the smelting slag with high zinc content as a secondary resource must be further processed and recycled to promote the sustainable development of the zinc industry in the future.
The zinc smelting waste residue treatment process mainly comprises four basic processes: roasting, leaching, purifying and electroextracting. However, when leaching zinc dross, other impurity ions, such as iron, cadmium and cobalt, inevitably enter the leachate along with the zinc. These impurity ions, particularly cobalt, can cause severe damage to the electrowinning of zinc.
Meanwhile, cobalt is widely applied to various products and process arrays, such as aviation, aerospace, electronics, batteries, alloys and the like. The consumption of cobalt is increased sharply in China, but the large cobalt ore resources are few in China, the taste is generally low, and the production quantity of the cobalt in China is far from meeting the demand. In contrast, some slags have a fairly high cobalt content. In addition, cobalt metal ions can cause toxicological disorders in human neurons, genetic toxicity and cancer, and their presence in the environment is also an important issue. These characteristics make the separation and recovery of cobalt from zinc dross equally important as zinc.
The zinc-cobalt separation widely adopts a solvent extraction method, zinc is extracted from a zinc-cobalt mixed solution or zinc and cobalt are simultaneously extracted by using a proper extracting agent, and then back extraction is carried out to achieve the aim of separating the zinc and the cobalt. The used cobalt and zinc separating extractants comprise fatty acid, D2EHPA, N235 extractants and the like, and sometimes two or more extractants are used for synergistic extraction. However, when the zinc content in the solution is too high, the extraction agent consumption is too large, and the separation efficiency is low. However, for solutions with a high zinc content, extractive separation is difficult to apply on an industrial scale.
Compared with an extraction method, the precipitation method is much simpler and more efficient, and is more suitable for industrial production, but the existing cobalt removal agents used in the precipitation method have some defects, such as high cost and low cobalt concentrate grade due to the adoption of beta-naphthol as the cobalt removal agent, and meanwhile, the amount of intermediate products in the treatment process is large, and the pH value of a reagent proportioning solution is not easy to control. The oxidation precipitant has the defects of large dosage, large change of removal rate caused by pH, poor selectivity and the like, for example, the cobalt precipitation amount of sodium hypochlorite is up to 20 times of the Co content in the leachate, and the cobalt precipitation can be carried out after manganese is preferentially precipitated. For zinc electrolyte, proper manganese ions can effectively ensure the quality and current efficiency of zinc, and if precipitation is preferred, manganese ions are additionally added.
The 'cobalt removal effect of ziram in zinc leachate' of corson discloses that ziram is used as a cobalt removal agent, has higher selectivity, mainly utilizes xanthate groups to combine with cobalt ions in a solution to generate a chelate, and can effectively realize the separation of the cobalt ions from zinc ions by utilizing the solubility product difference of precipitated substances. However, it can be seen from the literature that there are still many drawbacks, namely that the amount of zinc added is several hundred times the amount of cobalt, and that only low cobalt solutions can be treated. Another cobalt removal efficiency requires high acidity, the higher the acidity the better, however high acidity will lead to decomposition of ziram and thus the overall efficiency is not high.
So far, no cobalt remover which has high efficiency and high selectivity and is especially suitable for zinc smelting slag leachate exists.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide the cobalt removal agent and the application thereof.
In order to achieve the above object, the present invention adopts the following aspects.
The invention relates to a cobalt removing agent, which consists of dimethyl dithiocarbamate and sodium nitrite, wherein the mass ratio of the dimethyl dithiocarbamate is as follows: sodium nitrite 12-18: 1.
The invention provides a cobalt removing agent consisting of dimethyl dithiocarbamate and sodium nitrite for the first time, and the cobalt removing agent has the characteristics of high efficiency and strong selectivity. The dimethyl dithiocarbamate is not applied to cobalt removal, particularly cobalt removal of a high-cobalt zinc smelting slag leaching solution due to the problems of large dosage, low efficiency and the like when cobalt is independently precipitated, however, the cobalt removal effect is greatly improved only by adopting a small amount of sodium nitrite and the combination of the dimethyl dithiocarbamate in the invention, and the inventor finds that the cobalt still exists in a divalent form in the precipitation, so that the sodium nitrite plays an activating role rather than an oxidizing role in the combination of the cobalt removal agent, and the effect can be greatly improved only by adding a very small amount of the sodium nitrite. In fact, the inventor finds out through a large number of experiments that if the amount of the sodium nitrite is increased, the effect cannot be increased, but the effect is influenced.
In a preferred embodiment, the weight ratio of dimethyl dithiocarbamate: sodium nitrite 12-15: 1.
in a preferred embodiment, the dimethyldithiocarbamate is at least one selected from the group consisting of sodium dimethyldithiocarbamate (sodium dimethyl dithiocarbamate), potassium dimethyldithiocarbamate (potassium dimethyl dithiocarbamate), and zinc dimethyldithiocarbamate (zinc dimethyl dithiocarbamate).
As a further preference, the dimethyldithiocarbamate is selected from ziram.
In the technical scheme of the invention, the cobalt precipitation effect of the sodium thiram and the potassium thiram is also better, but the sodium thiram and the potassium thiram have slight taste and are similar to ammonia taste. In addition, if sodium and potassium ions enter the electrolyte, the aqueous solution needs to be recycled after electrolysis, the sodium and potassium ions are accumulated in the aqueous solution all the time, and the concentration of the sodium and potassium ions in the solution reaches dozens of grams per liter, and the sodium and potassium ions are crystallized out, so that the loss of the occluded zinc ions which are not electrolyzed is caused. Therefore, ziram is the most preferable scheme, and sodium nitrite in the formula of the invention is very small in dosage, so that the zinc electrolysis is hardly influenced.
The invention relates to an application of a cobalt removing agent, which is applied to a zinc smelting slag leachate for removing cobalt, wherein the zinc smelting slag leachate is subjected to iron removal and separation removal treatment to obtain a cobalt removing front solution, the cobalt removing agent is added into the cobalt removing front solution for reaction and solid-liquid separation to obtain a zinc electrolyte and a cobalt-containing precipitate;
the addition amount of the cobalt removing agent is 9-12 times of the total mass of cobalt in the cobalt removing front liquid.
Preferably, the concentration of zinc in the cobalt removal pre-solution is 100-140g/L, the concentration of cobalt is 0.4-0.8g/L, and the concentration of manganese is 2-3 g/L.
In a preferable scheme, the reaction temperature is 80-95 ℃ and the reaction time is 1-2 h.
In a preferred embodiment, the pH value of the reaction is controlled between 4 and 6.
In the technical scheme of the invention, the pH value is controlled to be between 4 and 6 with excellent efficiency, so that the decomposition failure of the ziram under the condition of too low pH value can be effectively avoided, and the pH value cannot be too high, and the zinc hydroxide precipitation is easily generated by hydrolysis due to too high concentration of zinc ions in the solution when the pH value is too high.
Preferably, the reaction is carried out under stirring at a speed of 500-700 rpm.
In a preferred scheme, the method for obtaining the leaching solution of the zinc smelting slag comprises the following steps: the method comprises the steps of leaching zinc smelting slag by using sulfuric acid as a leaching agent to obtain a leaching solution, namely a zinc smelting slag leaching solution, wherein the liquid-solid volume mass ratio of the sulfuric acid to the zinc smelting slag is 4-6ml:1g, the leaching temperature is 75-85 ℃, and the leaching time is 1-3 hours.
Further preferably, the concentration of the sulfuric acid is 1.5 to 2.5 mol/L.
As a further preference, the particle size of the zinc smelting slag is less than 40 meshes
Preferably, the iron removal mode of the zinc smelting slag leachate is that hydrogen peroxide is added to oxidize ferrous ions into ferric ions, and then the ferric ions are precipitated by adjusting the pH value to 2.5-4.5. In the process of removing iron from the zinc smelting slag leachate, the amount of the hydrogen peroxide is added by adopting the amount reported in the prior art, and the step is called as a neutralization hydrolysis method.
During zinc electrolysis, manganese dioxide is generated on the anode by divalent manganese ions, the manganese dioxide returns to the leaching-impurity removal-electrolysis process again in the form of anode mud, the concentration of the manganese ions needs to be kept balanced in the system, and when the concentration of the manganese ions in the solution is too low, manganese needs to be supplemented additionally. Therefore, after cobalt is removed by selecting some cobalt removing agents, manganese ions are required to be supplemented additionally, and in the technical scheme of the invention, the provided cobalt removing agents cannot precipitate the manganese ions, so that the manganese ions can be effectively ensured to be in a proper range. Of course, if the manganese ions in the leaching solution of the zinc smelting slag are too high, the method can add potassium permanganate to precipitate manganese after iron removal so as to restore the manganese concentration to the concentration required by electrolysis, and the adding amount of the potassium permanganate is determined by the proportion in the prior art, such as the ratio by mass of the potassium permanganate: the mass ratio of the manganese ions to be removed to the manganese ions is 1.5: 1.
in a preferred scheme, the cadmium removal mode of the zinc smelting slag leachate is zinc powder replacement.
In the technical scheme of the invention, the zinc powder replacement is carried out by adopting the conditions and parameters in the prior art.
Preferably, the cobalt-containing precipitate is subjected to heat treatment at 600-800 ℃ for 0.5-1.5h to obtain the cobalt slag. After heat treatment, the grade of cobalt in the obtained cobalt slag is more than or equal to 58 percent. It can be seen that the cobalt slag obtained by the invention has high grade and great recovery value.
Meanwhile, by the treatment of the scheme, the concentration of cobalt in the obtained zinc electrolyte is less than or equal to 1.5mg/L, and the removal rate (recovery rate) of cobalt is more than or equal to 99.7%. It can be seen that the invention can approximately remove all cobalt that is detrimental to zinc electrolysis.
In addition, the concentration of manganese in the obtained zinc electrolyte is unchanged, and the cobalt removing agent has high selectivity.
Action and Effect of the invention
The invention provides a cobalt removing agent, which is formed by compounding dimethyl dithiocarbamate and sodium nitrite, and is a high-efficiency and strong-selectivity cobalt removing agent.
Because dimethyldithiocarbamate has theoretical feasibility as a cobalt removal agent, but in practical application, a large number of problems exist, so that the dimethyldithiocarbamate cannot be really applied to practice, the inventor adopts a large number of substances to be compounded with dimethyldithiocarbamate, such as various oxidants, other precipitants, complexing agents and a large number of adjustment process parameters, so that good effects cannot be obtained, and finally unexpected effects can be obtained when sodium nitrite is found unexpectedly and a small amount of sodium nitrite is added.
The cobalt removing agent provided by the invention is applied to zinc smelting slag leachate for removing cobalt, the removal rate of cobalt is as high as more than 99.7%, namely cobalt can be almost completely removed, the concentration of cobalt in the solution completely meets the requirement of zinc electrolysis, and the cobalt removing agent has extremely high selectivity, manganese ions playing a role of protection electrolysis in the solution cannot be removed, in addition, in the cobalt removing process, the grade of cobalt slag obtained after heat treatment of the obtained cobalt precipitate is as high as more than 58%, and the cobalt removing agent has great recovery value.
Detailed Description
Example 1
Mixing 2mol/L sulfuric acid and zinc smelting slag in a proportion of 5: 1 liquid-solid ratio, heating and stirring for 2h, filtering to obtain a leaching solution, removing iron and cadmium ions by a neutralization hydrolysis method and a zinc powder replacement method respectively, and filtering to obtain a cobalt-removing pre-solution. The zinc concentration in the solution before cobalt removal is 110g/L, the cobalt concentration is 650mg/L, the manganese concentration is 2.4g/L, the pH value is adjusted to 4.5, 6g of thiram and 0.5g of sodium nitrite are added into 1L of the solution, the solution reacts for 2 hours at the stirring speed of 500 r/min at the temperature of 90 ℃, the filtration is carried out, the cobalt concentration in the filtrate is 1.3mg/L, the manganese concentration is basically unchanged, the cobalt recovery rate is 99.8 percent, the precipitation slag is dried after acid washing, and the cobalt taste is 13.8 percent. The cobalt precipitate is oxidized and roasted for 1 hour at the temperature of 600 ℃, and the grade of cobalt in the cobalt slag is 59.4 percent.
Example 2
Mixing 2mol/L sulfuric acid and zinc smelting slag in a proportion of 5: 1 liquid-solid ratio, heating and stirring for 2h, filtering to obtain a leaching solution, removing iron and cadmium ions by a neutralization hydrolysis method and a zinc powder replacement method respectively, and filtering to obtain a cobalt-removing pre-solution. The concentration of zinc in the solution before cobalt removal is 115g/L, the concentration of cobalt is 550mg/L, the concentration of manganese is 2.8g/L, the pH value is adjusted to 5, 5g of thiram and 0.4g of sodium nitrite are added into 1L of the solution, the solution reacts for 2 hours at the stirring speed of 500 r/min at the temperature of 90 ℃, the filtration is carried out, the concentration of cobalt in the filtrate is 1.5mg/L, the concentration of manganese is basically unchanged, the recovery rate of cobalt is 99.7 percent, the precipitated slag is dried after acid washing, and the taste of cobalt is 13.5 percent. The cobalt precipitate is oxidized and roasted for 1 hour at the temperature of 600 ℃, and the grade of the cobalt in the cobalt slag is 58.4 percent.
Example 3
Mixing 2mol/L sulfuric acid and zinc smelting slag in a proportion of 5: 1 liquid-solid ratio, heating and stirring for 2h, filtering to obtain a leaching solution, removing iron and cadmium ions by a neutralization hydrolysis method and a zinc powder replacement method respectively, and filtering to obtain a cobalt-removing pre-solution. The concentration of zinc in the solution before cobalt removal is 108g/L, the concentration of cobalt is 600mg/L, the concentration of manganese is 2.3g/L, the pH value is adjusted to 5, 6g of thiram and 0.4g of sodium nitrite are added into 1L of the solution, the solution reacts for 1.5 hours at the stirring speed of 500 r/min at the temperature of 90 ℃, the filtration is carried out, the concentration of cobalt in the filtrate is 1mg/L, the concentration of manganese is basically unchanged, the recovery rate of cobalt is 99.8 percent, the precipitation slag is dried after acid washing, and the taste of cobalt is 13.7 percent. The cobalt precipitate is oxidized and roasted for 1 hour at 800 ℃, and the grade of cobalt in the cobalt slag is 59.6 percent.
Example 4
Mixing 2mol/L sulfuric acid and zinc smelting slag in a proportion of 5: 1 liquid-solid ratio, heating and stirring for 2h, filtering to obtain a leaching solution, removing iron and cadmium ions by a neutralization hydrolysis method and a zinc powder replacement method respectively, and filtering to obtain a cobalt-removing pre-solution. The zinc concentration in the solution before cobalt removal is 106g/L, the cobalt concentration is 460mg/L, the manganese concentration is 2.7g/L, the pH value is adjusted to 4.8, 5g of thiram and 0.4g of sodium nitrite are added into 1L of the solution, the solution reacts for 2 hours at the stirring speed of 500 r/min at the temperature of 90 ℃, the filtration is carried out, the cobalt concentration in the filtrate is 0.9mg/L, the manganese concentration is basically unchanged, the cobalt recovery rate is 99.8 percent, the precipitation slag is acid-washed and dried, and the cobalt taste is 13.5 percent. The cobalt precipitate is oxidized and roasted for 1 hour at 700 ℃, and the grade of cobalt in the cobalt slag is 58.5 percent.
Example 6:
mixing 2mol/L sulfuric acid and zinc smelting slag in a proportion of 5: 1 liquid-solid ratio, heating and stirring for 2h, filtering to obtain a leaching solution, removing iron and cadmium ions by a neutralization hydrolysis method and a zinc powder replacement method respectively, and filtering to obtain a cobalt-removing pre-solution. The concentration of zinc in the solution is 117g/L, the concentration of cobalt is 680mg/L, the concentration of manganese is 2.5g/L, the pH value is adjusted to 5, 7g of thiram and 0.5g of sodium nitrite are added into 1L of the solution, the solution reacts for 2 hours at the stirring speed of 500 r/min at the temperature of 90 ℃, the filtration is carried out, the concentration of cobalt in the filtrate is 1.3mg/L, the concentration of manganese is basically unchanged, and the recovery rate of cobalt is 99.8%.
Comparative example 1
Mixing 2mol/L sulfuric acid and zinc smelting slag in a proportion of 5: 1 liquid-solid ratio, heating and stirring for 2h, filtering to obtain a leaching solution, removing iron and cadmium ions by a neutralization hydrolysis method and a zinc powder replacement method respectively, and filtering to obtain a cobalt-removing pre-solution. The concentration of zinc in the solution is 112g/L, the concentration of cobalt is 510mg/L, the concentration of manganese is 2.6g/L, the pH value is adjusted to 5, 5g of thiram is added into 1L of the solution, the solution reacts for 2 hours at the temperature of 90 ℃ and the stirring speed of 500 r/min, the filtration is carried out, the concentration of cobalt in the filtrate is 420mg/L, the concentration of manganese is basically unchanged, and the recovery rate of cobalt is 17.6%.
Comparative example 2
Mixing 2mol/L sulfuric acid and zinc smelting slag in a proportion of 5: 1 liquid-solid ratio, heating and stirring for 2h, filtering to obtain a leaching solution, removing iron and cadmium ions by a neutralization hydrolysis method and a zinc powder replacement method respectively, and filtering to obtain a cobalt-removing pre-solution. The concentration of zinc in the solution is 107g/L, the concentration of cobalt is 460mg/L, the concentration of manganese is 2.1g/L, the pH value is adjusted to 5, 5g of thiram and 0.4g of potassium permanganate are added into 1L of the solution, the solution reacts for 2 hours at the temperature of 90 ℃ and the stirring speed of 500 r/min, the filtration is carried out, the concentration of cobalt in the filtrate is 262mg/L, the concentration of manganese is 2.2g/L, and the cobalt recovery rate is 43 percent.
Comparative example 3
Mixing 2mol/L sulfuric acid and zinc smelting slag in a proportion of 5: 1 liquid-solid ratio, heating and stirring for 2h, filtering to obtain a leaching solution, removing iron and cadmium ions by a neutralization hydrolysis method and a zinc powder replacement method respectively, and filtering to obtain a cobalt-removing pre-solution. The concentration of zinc in the solution is 116g/L, the concentration of cobalt is 630mg/L, the concentration of manganese is 2.7g/L, the pH value is adjusted to 5, 8g of thiram and 50ml of hydrogen peroxide are added into 1L of the solution, the reaction is carried out for 2 hours at the temperature of 90 ℃ and the stirring speed of 500 r/min, the filtration is carried out, the concentration of cobalt in the filtrate is 353mg/L, the concentration of manganese is basically unchanged, and the recovery rate of cobalt is 44%.
Comparative example 4
Mixing 2mol/L sulfuric acid and zinc smelting slag in a proportion of 5: 1 liquid-solid ratio, heating and stirring for 2h, filtering to obtain a leaching solution, removing iron and cadmium ions by a neutralization hydrolysis method and a zinc powder replacement method respectively, and filtering to obtain a cobalt-removing pre-solution. The concentration of zinc in the solution is 109g/L, the concentration of cobalt is 590mg/L, the concentration of manganese is 2.4g/L, the pH value is adjusted to 5, 5g of thiram and 2.5g of sodium nitrite are added into 1L of the solution, the solution reacts for 2 hours at the temperature of 90 ℃ and the stirring speed of 500 r/min, the filtration is carried out, the concentration of cobalt in the filtrate is 165mg/L, the concentration of manganese is basically unchanged, and the recovery rate of cobalt is 72 percent.
Comparative example 5
Mixing 2mol/L sulfuric acid and zinc smelting slag in a proportion of 5: 1 liquid-solid ratio, heating and stirring for 2h, filtering to obtain a leaching solution, removing iron and cadmium ions by a neutralization hydrolysis method and a zinc powder replacement method respectively, and filtering to obtain a cobalt-removing pre-solution. The concentration of zinc in the solution is 113g/L, the concentration of cobalt is 480mg/L, the concentration of manganese is 2.5g/L, the pH value is adjusted to 1, 5g of thiram and 0.35g of sodium nitrite are added into 1L of the solution, the solution reacts for 2 hours at the temperature of 90 ℃ and the stirring speed of 500 r/min, the filtration is carried out, the concentration of cobalt in the filtrate is 307mg/L, the concentration of manganese is basically unchanged, and the recovery rate of cobalt is 36%.
Comparative example 6
Mixing 2mol/L sulfuric acid and zinc smelting slag in a proportion of 5: 1 liquid-solid ratio, heating and stirring for 2h, filtering to obtain a leaching solution, removing iron and cadmium ions by a neutralization hydrolysis method and a zinc powder replacement method respectively, and filtering to obtain a cobalt-removing pre-solution. The concentration of zinc in the solution is 110g/L, the concentration of cobalt is 438mg/L, the concentration of manganese is 2.8g/L, the pH value is adjusted to 4.5, 0.45g of thiram and 0.3g of sodium nitrite are added into 1L of the solution, the solution reacts for 2 hours at the temperature of 50 ℃ at the stirring speed of 500 r/min, the filtration is carried out, the concentration of cobalt in the filtrate is 390mg/L, the concentration of manganese is basically unchanged, and the recovery rate of cobalt is 11%.
In the above embodiment, the ion concentration in the solution can be measured by means of atomic absorption spectrophotometer or ICP (atomic emission spectroscopy). The invention can also adopt other testing means to detect the ion concentration.
Claims (9)
1. The cobalt removing agent is characterized by consisting of dimethyl dithiocarbamate and sodium nitrite, wherein the mass ratio of the dimethyl dithiocarbamate: sodium nitrite =12-18:1, and the dimethyldithiocarbamate is selected from ziram.
2. The cobalt remover according to claim 1, wherein the weight ratio of dimethyl dithiocarbamate: sodium nitrite = 12-15: 1.
3. the use of a cobalt-removing agent according to any one of claims 1-2, wherein the cobalt-removing agent is applied to a zinc smelting slag leachate to remove cobalt, the zinc smelting slag leachate is subjected to iron removal and separation treatment to obtain a cobalt-removing pre-solution, the cobalt-removing agent is added to the cobalt-removing pre-solution, and the cobalt-removing agent is reacted and subjected to solid-liquid separation to obtain a zinc electrolyte and a cobalt-containing precipitate;
the addition amount of the cobalt removing agent is 9-12 times of the total mass of cobalt in the cobalt removing front liquid.
4. Use of a cobalt remover according to claim 3,
the reaction temperature is 80-95 ℃ and the reaction time is 1-2 h; the pH value of the reaction is controlled between 4 and 6.
5. The use of a cobalt remover as claimed in claim 3, wherein the reaction is performed under stirring at a speed of 500-700 rpm.
6. The use of a cobalt removal agent as claimed in claim 3, wherein said zinc smelting slag leachate is obtained by the method comprising: the method comprises the steps of leaching zinc smelting slag by using sulfuric acid as a leaching agent to obtain a leaching solution, namely a zinc smelting slag leaching solution, wherein the liquid-solid volume mass ratio of the sulfuric acid to the zinc smelting slag is 4-6ml:1g, the leaching temperature is 75-85 ℃, and the leaching time is 1-3 hours.
7. The use of a cobalt removal agent as claimed in claim 6, wherein the concentration of said sulfuric acid is 1.5-2.5mol/L, and the particle size of said zinc slag is less than 40 mesh.
8. Use of a cobalt remover according to claim 3,
the iron removal mode of the zinc smelting slag leachate is that hydrogen peroxide is added to oxidize ferrous ions into ferric ions, and then the ferric ions are precipitated by adjusting the pH value to 2.5-4.5;
the cadmium removal mode of the zinc smelting slag leachate is zinc powder replacement.
9. The use of the cobalt remover as claimed in claim 3, wherein the cobalt-containing precipitate is heat treated at 600-800 ℃ for 0.5-1.5h to obtain cobalt slag.
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