CN110629039A - Deep purification method for zinc, cadmium and cobalt by wet smelting - Google Patents
Deep purification method for zinc, cadmium and cobalt by wet smelting Download PDFInfo
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Abstract
The invention discloses a method for deep purification of zinc, cadmium and cobalt smelted by a wet method, which comprises the following steps: taking zinc sulfate filtrate of zinc hydrometallurgy, heating and controlling acidity; measuring the content of cobalt and cadmium and calculating the using amount of a purifying agent; preparing a purifying agent solution; measuring the cobalt content and calculating the dosage of the activating agent; preparing an activator solution; the purifying agent and the activating agent solution react with the zinc sulfate filtrate; filtering to obtain new liquid, and determining whether the impurity content meets the specification. The method has excellent deep cadmium and cobalt removal efficiency, and has the advantages of low steam consumption, low cost, small added reagent amount, good stability in the reaction process, no redissolution of cadmium and cobalt impurities, improvement of the quality stability of the zinc sulfate solution, realization of deep purification of cadmium and cobalt in the zinc sulfate solution and remarkable economic benefit and environmental benefit due to the fact that the reaction temperature is lower than that of the conventional process.
Description
Technical Field
The invention belongs to the technical field of purification and impurity removal in the zinc hydrometallurgy industry, and particularly relates to a method for deep purification of zinc, cadmium and cobalt hydrometallurgy.
Background
Purification is an important step between leaching and electrolysis in a hydrometallurgical zinc process. At present, the content of impurities in zinc concentrate sold on the market is higher and higher, and the traditional purification method is difficult to realize deep purification. Most smelting plants at home and abroad commonly adopt an antimony salt purification process, wherein copper and cadmium are removed at a low temperature (50-60 ℃), cobalt and nickel are removed at a high temperature (more than 80 ℃) in a first section, and residual cadmium is removed at a medium temperature (60-70 ℃) in a third section. In order to solve the problem of cobalt removal of zinc sulfate solution in zinc hydrometallurgy, patent CN102839284B proposes a process for removing cadmium and cobalt from high cobalt zinc sulfate solution, wherein zinc powder is adopted for removing cadmium and cobalt, and the zinc powder is high in consumption and cost. Application number 201610148339.5 proposes a patent of adding manganese-based alloy powder containing 90% of manganese metal into a zinc sulfate solution to remove impurities such as copper, cadmium, cobalt, nickel and the like in the zinc sulfate solution in one step; CN106893872B proposes a three-stage purification process, and the purifying agent is alloy powder containing 30-49% of manganese. The zinc electrolysis efficiency can be influenced by a large amount of manganese ions entering a zinc sulfate solution system. In patent CN105483376A, cobalt remover A is prepared from glycine, cobalt remover B is prepared from sodium nitrite, and the mixture of cobalt remover A and cobalt remover B is used as cobalt remover, the concentration of sodium nitrite added in the method is 2-4 times of that of cobalt and iron, so that nitrate ions in the system are accumulated, and the anode plate of the main system is corroded.
Disclosure of Invention
The invention aims to provide a method for deep purification of zinc, cadmium and cobalt by wet smelting, which solves the problems of large zinc powder consumption, cadmium reproduction and redissolution, high cost and the like in the purification process, and improves the stability of the quality of a zinc sulfate solution, thereby realizing deep purification of cadmium and cobalt in the zinc sulfate solution.
In order to achieve the purpose, the invention adopts the technical scheme that:
a method for deep purification of zinc, cadmium and cobalt smelted by a wet method comprises the following steps:
(1) heating zinc sulfate filtrate obtained by zinc hydrometallurgy to 70-85 deg.C, and controlling acidity pH to 4.5-6.0; compared with the conventional process, the method has the advantages of low temperature requirement and low steam consumption;
(2) measuring the contents of cobalt and cadmium in the zinc sulfate filtrate, and calculating the dosage of a purifying agent:
cleaning agent dosage = (Co)2+/59+Cd2+/112)×C1×R1×V；
Wherein, Co2+The cobalt content (mg/L) in the zinc sulfate filtrate;
Cd2+the cadmium content (mg/L) in the zinc sulfate filtrate;
C1relative atomic mass of scavenger;
R1is a reaction coefficient, R is more than or equal to 21≤8；
V is the volume of zinc sulfate filtrate;
(3) weighing a purifying agent according to the using amount of the purifying agent calculated in the step (2), and dissolving the purifying agent with water until the concentration of the purifying agent is 10-40% to obtain a purifying agent solution;
(4) determining the cobalt content in the zinc sulfate filtrate, and calculating the dosage of an activating agent:
activator amount = Co2+/59×C2×R2×V；
Wherein, Co2+The cobalt content (mg/L) in the zinc sulfate filtrate;
C2relative molecular mass of activator;
R2is coefficient, R is more than or equal to 0.52≤2；
V is the volume of zinc sulfate filtrate;
(5) weighing the activator according to the dosage of the activator calculated in the step (4), and dissolving the activator with water until the concentration of the activator is 10-40% to obtain an activator solution;
(6) respectively adding the purifying agent solution and the activating agent solution obtained in the steps (3) and (5) into the zinc sulfate filtrate, stirring at 76-85 r/min, and reacting at 70-85 ℃ for 1-1.5 h; the purifying agent adopted by the invention is a broad-spectrum heavy metal precipitator, can react with various heavy metal ions (such as copper, cadmium, cobalt, nickel, zinc and the like) in the zinc sulfate solution to generate chelate salt precipitate, can deeply remove other impurities such as residual copper, nickel and the like in the solution while deeply removing cadmium and cobalt, and obviously improves the impurity removal effect of the zinc sulfate solution; the activator adopted by the invention can form a cobalt complex with cobalt ions, so that divalent cobalt ions are oxidized into trivalent cobalt ions, the trivalent cobalt ions and the purifying agent form a chelate precipitate with smaller solubility product and more stability, the deep separation of the cobalt ions is realized, the cobalt content can be reduced to be below 0.3mg/L from 40-90mg/L, and the electrolysis requirements of 24h and 48h are met;
(7) and after the reaction is finished, filtering to obtain a new liquid, and determining whether the main impurity content of the new liquid meets the specification.
In order to further realize the invention, the purifiers are alkali metal thiocarbamates with different carbon chain substituents.
To further carry out the invention, the scavenger is sodium dimethyldithiocarbamate, potassium dimethyldithiocarbamate, zinc dimethyldithiocarbamate, sodium diethyldithiocarbamate, potassium diethyldithiocarbamate or zinc diethyldithiocarbamate.
In order to further realize the invention, the purifying agent is sodium dimethyldithiocarbamate.
To further realize the present invention, the activator is an alkali metal nitrite.
In order to further realize the invention, the activating agent is one or a mixture of two of sodium nitrite and potassium nitrite.
To further realize the present invention, the activating agent is sodium nitrite.
In order to further realize the invention, the zinc sulfate filtrate mainly comprises the following components: zn 130-160g/L, Cu-0.5 mg/L, Cd-50 mg/L, Co-80 mg/L, Ni-30 mg/L, Fe-20 mg/L, As-0.2 mg/L, Sb-0.2 mg/L, Ge-0.2 mg/L.
In order to further realize the invention, the control indexes of the new liquid are as follows: cd is less than or equal to 0.5mg/L, Co is less than or equal to 0.5mg/L, and the content of other metal ions meets the zinc electrodeposition requirement.
Compared with the prior art, the invention has the beneficial effects that:
the method has excellent deep cadmium and cobalt removal efficiency, and has the advantages of low steam consumption, low cost, small added reagent amount, good stability in the reaction process, no redissolution of cadmium and cobalt impurities, improvement of the quality stability of the zinc sulfate solution, realization of deep purification of cadmium and cobalt in the zinc sulfate solution and remarkable economic benefit and environmental benefit due to the fact that the reaction temperature is lower than that of the conventional process.
Detailed Description
The present invention will be further described with reference to the following embodiments.
A method for deep purification of zinc, cadmium and cobalt smelted by a wet method comprises the following steps:
(1) taking zinc sulfate filtrate of zinc hydrometallurgy, heating to 70-85 ℃, controlling the acidity pH to 4.5-6.0, wherein the zinc sulfate filtrate mainly comprises the following components: zn 130-160g/L, Cu-0.5 mg/L, Cd-50 mg/L, Co-80 mg/L, Ni-30 mg/L, Fe-20 mg/L, As-0.2 mg/L, Sb-0.2 mg/L, Ge-0.2 mg/L;
(2) measuring the contents of cobalt and cadmium in the zinc sulfate filtrate, and calculating the dosage of a purifying agent:
cleaning agent dosage = (Co)2+/59+Cd2+/112)×C1×R1×V；
Wherein, Co2+The cobalt content (mg/L) in the zinc sulfate filtrate;
Cd2+the cadmium content (mg/L) in the zinc sulfate filtrate;
C1relative atomic mass of scavenger;
R1is a reaction coefficient, R is more than or equal to 21≤8；
V is the volume of zinc sulfate filtrate;
(3) weighing a purifying agent according to the using amount of the purifying agent calculated in the step (2), and dissolving the purifying agent with water until the concentration of the purifying agent is 10-40% to obtain a purifying agent solution;
(4) determining the cobalt content in the zinc sulfate filtrate, and calculating the dosage of an activating agent:
activator amount = Co2+/59×C2×R2×V；
Wherein, Co2+The cobalt content (mg/L) in the zinc sulfate filtrate;
C2relative molecular mass of activator;
R2is coefficient, R is more than or equal to 0.52≤2；
V is the volume of zinc sulfate filtrate;
(5) weighing the activator according to the dosage of the activator calculated in the step (4), and dissolving the activator with water until the concentration of the activator is 10-40% to obtain an activator solution;
(6) respectively adding the purifying agent solution and the activating agent solution obtained in the steps (3) and (5) into the zinc sulfate filtrate, stirring at 76-85 r/min, and reacting at 70-85 ℃ for 1-1.5 h;
(7) after the reaction is finished, filtering to obtain a new liquid, and determining whether the main impurity content of the new liquid meets the specification, wherein the control indexes of the new liquid are as follows: cd is less than or equal to 0.5mg/L, Co is less than or equal to 0.5mg/L, and the content of other metal ions meets the zinc electrodeposition requirement.
The purifying agent is alkali metal thiocarbamate salts with different carbon chain substituents, namely sodium dimethyldithiocarbamate, potassium dimethyldithiocarbamate, zinc dimethyldithiocarbamate, sodium diethyldithiocarbamate, potassium diethyldithiocarbamate or zinc diethyldithiocarbamate, and preferably the purifying agent is sodium dimethyldithiocarbamate.
The activating agent is alkali metal nitrite, namely one or a mixture of two of sodium nitrite and potassium nitrite, preferably sodium nitrite.
Example 1:
a method for deep purification of zinc, cadmium and cobalt smelted by a wet method comprises the following steps:
(1) taking 1.6L of zinc sulfate filtrate obtained by zinc hydrometallurgy, heating to 70-85 ℃, controlling the acidity pH to be 5.0, and determining that the zinc sulfate filtrate mainly comprises the following components: zn 135g/L, Cu 0.1mg/L, Cd 40mg/L, Co 45mg/L, Ni 8mg/L, Fe 8mg/L and As0.09mg/L, Sb 0.01.01 mg/L, Ge 0.01.01 mg/L;
(2) determining the contents of cobalt and cadmium in the zinc sulfate filtrate as Co 45mg/L and Cd 40mg/L respectively, and calculating the dosage of the purifying agent sodium dimethyldithiocarbamate:
sodium dimethyldithiocarbamate in amount = (Co)2+/59+Cd2+/112)×C1×R1×V
=(45/59+40/112)×143×5×1.6
=1281.3mg
Wherein, Co2+The cobalt content (mg/L) in the zinc sulfate filtrate;
Cd2+the cadmium content (mg/L) in the zinc sulfate filtrate;
C1relative atomic mass of sodium dimethyldithiocarbamate as scavenger, C1=143；
R1As a coefficient of reaction, R1Taking a value of 5;
v is the volume of zinc sulfate filtrate;
(3) dissolving a purifying agent sodium dimethyldithiocarbamate with industrial water according to the concentration of 20 percent to obtain a purifying agent sodium dimethyldithiocarbamate solution;
(4) measuring the cobalt content in the zinc sulfate filtrate to calculate the using amount of the activating agent sodium nitrite:
sodium nitrite usage = Co2+/59×C2×R2×V=45/59×69×0.5×1.6=42.1mg
Wherein, Co2+The cobalt content (mg/L) in the zinc sulfate filtrate;
C2molecular mass of sodium nitrite as activator, C2=69；
R2Is a coefficient, R2=0.5；
V is the volume of zinc sulfate filtrate;
(5) dissolving an activating agent sodium nitrite with industrial water according to the concentration of 20 percent to obtain an activating agent sodium nitrite solution;
(6) adding a sodium dimethyldithiocarbamate solution and a sodium nitrite solution into the zinc sulfate filtrate, stirring at 76 r/min, and reacting at 70-85 ℃ for 1.5 h;
(7) after the reaction is finished, filtering to obtain a new liquid, and determining the main impurity content of the new liquid: cu 0.04mg/L, Cd 0.1mg/L and Co 0.3mg/L, and the content of other metal ions meets the zinc electrodeposition requirement.
A method for deep purification of zinc, cadmium and cobalt smelted by a wet method comprises the following steps:
(1) taking 1.6L of zinc sulfate filtrate obtained by zinc hydrometallurgy, heating to 85 ℃, controlling the acidity pH to be 6.0, and determining the main components of the zinc sulfate filtrate as follows: zn 135g/L, Cu 0.1mg/L, Cd 40mg/L, Co 45mg/L, Ni 8mg/L, Fe 8mg/L and As0.09mg/L, Sb 0.01.01 mg/L, Ge 0.01.01 mg/L;
(2) determining the contents of cobalt and cadmium in the zinc sulfate filtrate as Co 45mg/L and Cd 40mg/L respectively, and calculating the dosage of the purifying agent potassium dimethyldithiocarbamate:
amount of potassium dimethyldithiocarbamate = (Co)2+/59+Cd2+/112)×C1×R1×V
=(45/59+40/112)×195×5×1.6
=1747.0mg
Wherein, Co2+The cobalt content (mg/L) in the zinc sulfate filtrate;
Cd2+the cadmium content (mg/L) in the zinc sulfate filtrate;
C1relative atomic mass of potassium dimethyldithiocarbamate as scavenger, C1=195；
R1As a coefficient of reaction, R1Taking a value of 5;
v is the volume of zinc sulfate filtrate;
(3) dissolving a purifying agent potassium dimethyldithiocarbamate by using industrial water according to the concentration of 20 percent to obtain a purifying agent potassium dimethyldithiocarbamate solution;
(4) measuring the cobalt content in the zinc sulfate filtrate to calculate the using amount of the activating agent sodium nitrite:
sodium nitrite usage = Co2+/59×C2×R2×V=45/59×69×0.5×1.6=42.1mg
Wherein, Co2+The cobalt content (mg/L) in the zinc sulfate filtrate;
C2molecular mass of sodium nitrite as activator, C2=69；
R2Is a coefficient, R2=0.5；
V is the volume of zinc sulfate filtrate;
(5) dissolving an activating agent sodium nitrite with industrial water according to the concentration of 20 percent to obtain an activating agent sodium nitrite solution;
(6) adding a potassium dimethyldithiocarbamate solution and a sodium nitrite solution into the zinc sulfate filtrate, stirring at 85 revolutions per minute, and reacting at 85 ℃ for 1.5 hours;
(7) after the reaction is finished, filtering to obtain a new liquid, and determining the main impurity content of the new liquid: cu 0.05mg/L, Cd 0.2mg/L and Co 0.3mg/L, and the content of other metal ions meets the zinc electrodeposition requirement.
Example 3:
a method for deep purification of zinc, cadmium and cobalt smelted by a wet method comprises the following steps:
(1) taking 1.6L of zinc sulfate filtrate obtained by zinc hydrometallurgy, heating to 85 ℃, controlling the acidity pH to be 6.0, and determining the main components of the zinc sulfate filtrate as follows: zn 135g/L, Cu 0.1mg/L, Cd 42mg/L, Co 40mg/L, Ni 8mg/L, Fe 8mg/L and As0.09mg/L, Sb 0.01.01 mg/L, Ge 0.01.01 mg/L;
(2) determining the contents of cobalt and cadmium in the zinc sulfate filtrate as Co 40mg/L and Cd 42mg/L respectively, and calculating the dosage of the purifying agent zinc dimethyldithiocarbamate:
amount of zinc dimethyldithiocarbamate = (Co)2+/59+Cd2+/112)×C1×R1×V
=(40/59+42/112)×306×5×1.6
=2577.7mg
Wherein, Co2+The cobalt content (mg/L) in the zinc sulfate filtrate;
Cd2+the cadmium content (mg/L) in the zinc sulfate filtrate;
C1relative atomic mass of zinc dimethyldithiocarbamate as scavenger, C1=306；
R1As a coefficient of reaction, R1Taking a value of 5;
v is the volume of zinc sulfate filtrate;
(3) dissolving a purifying agent zinc dimethyldithiocarbamate with industrial water according to the concentration of 30% to obtain a purifying agent zinc dimethyldithiocarbamate solution;
(4) measuring the cobalt content in the zinc sulfate filtrate to calculate the using amount of the activating agent potassium nitrite:
potassium nitrite usage = Co2+/59×C2×R2×V=40/59×85×0.5×1.6=46.1mg
Wherein, Co2+The cobalt content (mg/L) in the zinc sulfate filtrate;
C2as activator of the molecular mass of potassium nitrite, C2=85；
R2Is a coefficient, R2=0.5；
V is the volume of zinc sulfate filtrate;
(5) dissolving an activating agent potassium nitrite with industrial water according to the concentration of 30 percent to obtain an activating agent potassium nitrite solution;
(6) adding a zinc dimethyldithiocarbamate solution and a potassium nitrite solution into the zinc sulfate filtrate, stirring at 80 revolutions per minute, and reacting for 1.5 hours at 80 ℃;
(7) after the reaction is finished, filtering to obtain a new liquid, and determining the main impurity content of the new liquid: cu 0.05mg/L, Cd 0.3mg/L and Co 0.3mg/L, and the content of other metal ions meets the zinc electrodeposition requirement.
Example 4:
a method for deep purification of zinc, cadmium and cobalt smelted by a wet method comprises the following steps:
(1) taking 1.6L of zinc sulfate filtrate obtained by zinc hydrometallurgy, heating to 80 ℃, controlling the acidity pH to be 5.0, and determining the main components of the zinc sulfate filtrate as follows: zn 135g/L, Cu 0.1mg/L, Cd 42mg/L, Co 40mg/L, Ni 8mg/L, Fe 8mg/L and As0.09mg/L, Sb 0.01.01 mg/L, Ge 0.01.01 mg/L;
(2) determining the contents of cobalt and cadmium in the zinc sulfate filtrate as Co 40mg/L and Cd 42mg/L respectively, and calculating the dosage of the purifying agent sodium diethyldithiocarbamate:
sodium diethyldithiocarbamate amount = (Co)2+/59+Cd2+/112)×C1×R1×V
=(40/59+42/112)×225×8×1.6
=3032.6mg
Wherein, Co2+The cobalt content (mg/L) in the zinc sulfate filtrate;
Cd2+the cadmium content (mg/L) in the zinc sulfate filtrate;
C1relative atomic mass of sodium diethyldithiocarbamate as scavenger, C1=225；
R1As a coefficient of reaction, R1Taking a value of 8;
v is the volume of zinc sulfate filtrate;
(3) dissolving a purifying agent sodium diethyldithiocarbamate with industrial water according to the concentration of 40% to obtain a purifying agent sodium diethyldithiocarbamate solution;
(4) measuring the cobalt content in the zinc sulfate filtrate to calculate the using amount of the activating agent potassium nitrite:
potassium nitrite usage = Co2+/59×C2×R2×V=40/59×85×2×1.6=184.4mg
Wherein, Co2+The cobalt content (mg/L) in the zinc sulfate filtrate;
C2as activator of the molecular mass of potassium nitrite, C2=85；
R2Is a coefficient, R2=2；
V is the volume of zinc sulfate filtrate;
(5) dissolving an activating agent potassium nitrite with industrial water according to the concentration of 40% to obtain an activating agent potassium nitrite solution;
(6) adding sodium diethyldithiocarbamate solution and potassium nitrite solution into zinc sulfate filtrate, stirring at 80 r/min, and reacting at 80 deg.C for 1.5 h;
(7) after the reaction is finished, filtering to obtain a new liquid, and determining the main impurity content of the new liquid: cu 0.05mg/L, Cd 0.2mg/L and Co 0.2mg/L, and the content of other metal ions meets the zinc electrodeposition requirement.
Example 5:
a method for deep purification of zinc, cadmium and cobalt smelted by a wet method comprises the following steps:
(1) taking 1.6L of zinc sulfate filtrate obtained by zinc hydrometallurgy, heating to 80 ℃, controlling the acidity pH to be 5.0, and determining the main components of the zinc sulfate filtrate as follows: zn 140g/L, Cu 0.1mg/L, Cd 46mg/L, Co 41mg/L, Ni 8mg/L, Fe 8mg/L and As0.09mg/L, Sb 0.01.01 mg/L, Ge 0.01.01 mg/L;
(2) determining the contents of cobalt and cadmium in the zinc sulfate filtrate as Co 41mg/L and Cd 46mg/L respectively, and calculating the dosage of the purifying agent potassium diethyldithiocarbamate:
amount of potassium diethyldithiocarbamate = (Co)2+/59+Cd2+/112)×C1×R1×V
=(41/59+46/112)×241×4×1.6
=1705.3mg
Wherein, Co2+The cobalt content (mg/L) in the zinc sulfate filtrate;
Cd2+the cadmium content (mg/L) in the zinc sulfate filtrate;
C1relative atomic mass of Potassium Diethyldithiocarbamate as scavenger, C1=241；
R1As a coefficient of reaction, R1Taking a value of 4;
v is the volume of zinc sulfate filtrate;
(3) dissolving a purifying agent potassium diethyldithiocarbamate by using industrial water according to the concentration of 15% to obtain a purifying agent potassium diethyldithiocarbamate solution;
(4) measuring the cobalt content in the zinc sulfate filtrate to calculate the dosage of the activating agent (sodium nitrite and potassium nitrite 1: 1):
sodium nitrite usage = Co2+/59×C2×R2×V=41/59×69×0.5×1.6=38.4mg
Wherein, Co2+The cobalt content (mg/L) in the zinc sulfate filtrate;
C2molecular mass of sodium nitrite as activator, C2=69；
R2Is a coefficient, R2=0.5；
V is the volume of zinc sulfate filtrate;
potassium nitrite usage = Co2+/59×C2×R2×V=41/59×85×0.5×1.6=47.25mg
Wherein, Co2+The cobalt content (mg/L) in the zinc sulfate filtrate;
C2as activator of the molecular mass of potassium nitrite, C2=85；
R2Is a coefficient, R2=0.5；
V is the volume of zinc sulfate filtrate;
(5) dissolving activating agents of potassium nitrite and sodium nitrite in industrial water according to the concentration of 15% to obtain a mixed solution of the activating agents of the sodium nitrite and the potassium nitrite;
(6) adding the potassium diethyldithiocarbamate solution, the mixed solution of sodium nitrite and potassium nitrite into the zinc sulfate filtrate, stirring at 80 revolutions per minute, and reacting at 80 ℃ for 1.5 hours;
(7) after the reaction is finished, filtering to obtain a new liquid, and determining the main impurity content of the new liquid: cu 0.04mg/L, Cd 0.3mg/L and Co 0.3mg/L, and the content of other metal ions meets the zinc electrodeposition requirement.
Example 6:
a method for deep purification of zinc, cadmium and cobalt smelted by a wet method comprises the following steps:
(1) taking 1.6L of zinc sulfate filtrate obtained by zinc hydrometallurgy, heating to 80 ℃, controlling the acidity pH to be 5.0, and determining the main components of the zinc sulfate filtrate as follows: zn 140g/L, Cu 0.1mg/L, Cd 46mg/L, Co 41mg/L, Ni 8mg/L, Fe 8mg/L and As0.09mg/L, Sb 0.01.01 mg/L, Ge 0.01.01 mg/L;
(2) determining the contents of cobalt and cadmium in the zinc sulfate filtrate as Co 41mg/L and Cd 46mg/L respectively, and calculating the dosage of the purifying agent zinc diethyldithiocarbamate:
amount of zinc diethyldithiocarbamate = (Co)2+/59+Cd2+/112)×C1×R1×V
=(41/59+46/112)×362×4×1.6
=2561.5mg
Wherein, Co2+The cobalt content (mg/L) in the zinc sulfate filtrate;
Cd2+the cadmium content (mg/L) in the zinc sulfate filtrate;
C1relative atomic mass of zinc diethyldithiocarbamate as scavenger, C1=362；
R1As a coefficient of reaction, R1Taking a value of 4;
v is the volume of zinc sulfate filtrate;
(3) dissolving a purifying agent zinc diethyldithiocarbamate by using industrial water according to the concentration of 15% to obtain a purifying agent zinc diethyldithiocarbamate solution;
(4) measuring the cobalt content in the zinc sulfate filtrate to calculate the using amount of the activating agent sodium nitrite:
sodium nitrite usage = Co2+/59×C2×R2×V=41/59×69×0.5×1.6=38.4mg
Wherein, Co2+The cobalt content (mg/L) in the zinc sulfate filtrate;
C2molecular mass of sodium nitrite as activator, C2=69；
R2Is a coefficient, R2=0.5；
V is the volume of zinc sulfate filtrate;
(5) dissolving an activating agent sodium nitrite with industrial water according to the concentration of 15% to obtain an activating agent sodium nitrite solution;
(6) adding zinc diethyldithiocarbamate solution and sodium nitrite solution into zinc sulfate filtrate, stirring at 80 r/min, and reacting at 80 deg.C for 1.5 h;
(7) after the reaction is finished, filtering to obtain a new liquid, and determining the main impurity content of the new liquid: cu 0.05mg/L, Cd 0.2mg/L and Co 0.3mg/L, and the content of other metal ions meets the zinc electrodeposition requirement.
Claims (9)
1. A method for deep purification of zinc, cadmium and cobalt smelted by a wet method is characterized by comprising the following steps:
(1) heating zinc sulfate filtrate obtained by zinc hydrometallurgy to 70-85 deg.C, and controlling acidity pH to 4.5-6.0;
(2) measuring the contents of cobalt and cadmium in the zinc sulfate filtrate, and calculating the dosage of a purifying agent:
cleaning agent dosage = (Co)2+/59+Cd2+/112)×C1×R1×V；
Wherein, Co2+The cobalt content (mg/L) in the zinc sulfate filtrate;
Cd2+the cadmium content (mg/L) in the zinc sulfate filtrate;
C1relative atomic mass of scavenger;
R1is a reaction coefficient, R is more than or equal to 21≤8；
V is the volume of zinc sulfate filtrate;
(3) weighing a purifying agent according to the using amount of the purifying agent calculated in the step (2), and dissolving the purifying agent with water until the concentration of the purifying agent is 10-40% to obtain a purifying agent solution;
(4) determining the cobalt content in the zinc sulfate filtrate, and calculating the dosage of an activating agent:
activator amount = Co2+/59×C2×R2×V；
Wherein, Co2+The cobalt content (mg/L) in the zinc sulfate filtrate;
C2relative molecular mass of activator;
R2is coefficient, R is more than or equal to 0.52≤2；
V is the volume of zinc sulfate filtrate;
(5) weighing the activator according to the dosage of the activator calculated in the step (4), and dissolving the activator with water until the concentration of the activator is 10-40% to obtain an activator solution;
(6) respectively adding the purifying agent solution and the activating agent solution obtained in the steps (3) and (5) into the zinc sulfate filtrate, stirring at 76-85 r/min, and reacting at 70-85 ℃ for 1-1.5 h;
(7) and after the reaction is finished, filtering to obtain a new liquid, and determining whether the main impurity content of the new liquid meets the specification.
2. The method for deep purification of zinc, cadmium and cobalt by wet smelting as claimed in claim 1, wherein: the purificant is an alkali metal thiocarbamate with different carbon chain substituents.
3. The method for deep purification of zinc, cadmium and cobalt by wet smelting as claimed in claim 1 or 2, characterized in that: the purifying agent is sodium dimethyldithiocarbamate, potassium dimethyldithiocarbamate, zinc dimethyldithiocarbamate, sodium diethyldithiocarbamate, potassium diethyldithiocarbamate or zinc diethyldithiocarbamate.
4. The method for deep purification of zinc, cadmium and cobalt by wet smelting as claimed in claim 3, wherein: the purifying agent is sodium dimethyldithiocarbamate.
5. The method for deep purification of zinc, cadmium and cobalt by wet smelting as claimed in claim 1, wherein: the activating agent is an alkali metal nitrite.
6. The method for deep purification of zinc, cadmium and cobalt by wet smelting as claimed in claim 1 or 5, characterized in that: the activating agent is one or a mixture of two of sodium nitrite and potassium nitrite.
7. The method for deep purification of zinc, cadmium and cobalt by wet smelting as claimed in claim 6, wherein: the activating agent is sodium nitrite.
8. The method for deep purification of zinc, cadmium and cobalt by wet smelting as claimed in claim 1, wherein: the zinc sulfate filtrate mainly comprises the following components: zn 130-160g/L, Cu-0.5 mg/L, Cd-50 mg/L, Co-80 mg/L, Ni-30 mg/L, Fe-20 mg/L, As-0.2 mg/L, Sb-0.2 mg/L, Ge-0.2 mg/L.
9. The method for deep purification of zinc, cadmium and cobalt by wet smelting as claimed in claim 1, wherein: the control indexes of the new liquid are as follows: cd is less than or equal to 0.5mg/L, Co is less than or equal to 0.5mg/L, and the content of other metal ions meets the zinc electrodeposition requirement.
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