CN111676490A - Method for optimizing zinc electrodeposition process - Google Patents
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
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- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/16—Electrolytic production, recovery or refining of metals by electrolysis of solutions of zinc, cadmium or mercury
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
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Abstract
The invention relates to a method for optimizing zinc electrodeposition process, which properly thins Zn by using Lorentz force generated by a magnetic field2+And the thickness of chemical hydration layer of other positive and negative ions, reduce the size of hydrone cluster; then the Zn is thinned again by utilizing the magnetic field gradient force generated by the magnetic field2+The thickness of the chemical hydration layer is reduced, the size of the hydrone cluster is reduced, and H is increased+、Mn2+、Cu2+、Fe2+、Fe3+、Ge4+、Ni2+、Co2+、Ca2+、Mg2+The thickness of the hydration layer of the plasma paramagnetic ions is reduced, so that the voltage drop of the electrodeposition tank is reduced, and H is increased+The overvoltage of the cathode can reduce the formation of calcium sulfate and magnesium sulfate and reduce the occurrence of plate burning and back melting of cathode zinc. The invention can improve the quality of the electrodeposited zinc without adding extra chemical reagents, hinder the anode corrosion and achieve the purposes of energy saving and consumption reduction.
Description
Technical Field
The invention belongs to the technical field of zinc electrodeposition, and particularly relates to a method for optimizing a zinc electrodeposition process.
Background
In the zinc hydrometallurgy electrodeposition process, the most concerned problem is the consumption of electric energy. Around the energy saving and consumption reduction of the zinc electrolysis process, a lot of students and zinc manufacturers carry out a lot of work. The direct current unit consumption of zinc electrodeposition is related to two factors, namely current efficiency and cell voltage. The dc current consumption is inversely proportional to the current efficiency and directly proportional to the cell voltage. Therefore, all measures capable of improving the current efficiency and reducing the cell voltage can reduce the direct current unit consumption of zinc electrodeposition, and through analysis of a large amount of industrial test data and graphic data, factors influencing the zinc electrodeposition current efficiency, including the current density of a cathode plate, the concentration of zincic acid in electrolyte, the temperature of the electrolyte, the impurity content and variety in the electrolyte, the surface state of separated zinc and the electrolysis period, can be obtained. The specific influence of the factors on zinc electrodeposition energy consumption is as follows:
(1) zincic acid concentration of electrolyte
The main components of the electrolyte are zinc ions and sulfuric acid, and the zinc acid concentration of the electrolyte in the electrolyte is stabilized, so that the basic condition for normally carrying out electrolysis is provided. Under the condition of certain other conditions, the current efficiency is reduced along with the reduction of the zinc content in the electrolyte and the increase of the acid content in the electrolyte, and the current efficiency is increased along with the increase of the zinc content in the electrolyte and the reduction of the acid content in the electrolyte. This is because the concentration of sulfuric acid is relatively increased when the zinc content is too low or the acid content is too high, and the concentration polarization phenomenon occurs in the zinc ion concentration near the cathode, so that the zinc precipitated on the cathode is re-dissolved, and the electrode potential for hydrogen precipitation is also decreased with the decrease in the zinc ion concentration in the solution, so that the possibility of hydrogen precipitation on the cathode is increased.
(2) Current density of cathode plate
The current density is defined as the ratio of the current intensity to the plate area. The hydrogen overvoltage increases with increasing area current, which is generally advantageous for increasing the current efficiency and to obtain crystalline, dense metallic zinc, but must be matched by a corresponding electrolyte composition and lower temperature conditions. The increase of the area current also increases the resistance voltage drop of the electrolyte and raises the temperature, thus accelerating the precipitation of impurities.
(3) Impurity content in electrolyte
The impurity content in the electrolyte has a great influence on the energy consumption of zinc electrodeposition, and all the metal impurities which can reduce hydrogen overvoltage and form a micro-battery reaction positive electrical property by taking zinc as an anode in the electrolyte can increase the energy consumption of the zinc electrodeposition, and can cause the phenomena of plate burning, zinc precipitation, re-dissolution and the like which are not beneficial to production. Generally, the impurity content of the electrolyte is mainly controlled in a purification step, and the electrolysis process utilizes a purified and qualified electrolyte, but the deep purification is difficult to achieve at the present stage.
Therefore, from the foregoing analysis, it can be understood that the higher the current density, the greater the power consumption. This is because in this case the cell voltage increases significantly as a result. However, if the current density is too small, the yield is lowered, the current efficiency is low, and the power consumption is also not small. The current efficiency increases with decreasing electrolyte temperature, but the cell voltage decreases with increasing temperature. The electric energy consumption is reduced along with the increase of the current density of the electrolysis in the zinc electrodeposition process, and the electric energy consumption is increased again after reaching a certain limit. The higher the current density of the electrolytic deposition, the higher the allowable acid content in the electrolyte. When the electrolyte contains low acid, the electrolyte has high resistance, so that the electric energy consumption is high. When the acid content of the electrolyte is larger than a certain value, the electric energy consumption is increased due to the obvious reduction of the current efficiency. Through the comprehensive analysis of the factors influencing the cell voltage and the current efficiency, the fact that the current efficiency is improved and the cell voltage is reduced is often contradictory. Therefore, under the premise of ensuring the product quality, the technical conditions of reducing the cell voltage and improving the current efficiency as much as possible are used for analyzing the problem of syndrome differentiation so as to achieve the purpose of reducing the electric energy consumption. In the actual production process, in order to stabilize the production and reduce the electricity cost, a plurality of conditions are basically kept constant, and the zinc electrodeposition process is difficult to optimize in the prior art, so the invention provides the zinc electrodeposition process optimized by the strong magnetic treatment technology.
Disclosure of Invention
It is an object of the present invention to provide a method for optimizing zinc electrodeposition processes that reduces the formation of calcium sulfate and magnesium sulfate, and reduces the occurrence of cathode zinc burn-out and meltback.
In order to achieve the aim, the invention discloses a method for optimizing a zinc electrodeposition process, which is characterized by comprising the following steps of: step 1: measuring Zn in electric liquid2+、H2SO4And the concentration of other impurity ions, connecting the magnetizer to the liquid inlet pipe of the electrolytic bath, leading the electrolyte to be firstly acted by Lorentz force through the magnetizer and then acted by magnetic field gradient force, wherein the magnetic induction intensity for generating the Lorentz force is 1-1.5T, the magnetic induction intensity for providing the magnetic field gradient force is 2-3T, when the electrolyte passes through the magnetic field for providing the Lorentz force, a pipeline adopts a flow dividing measure, namely 1 set of magnetic field for providing the Lorentz force needs to be matched with 2 sets of magnetic field for providing the magnetic field gradient force, the flow rate of the electrolyte passing through the magnetizer for providing the Lorentz force is 120-fold and 240L/min, the flow rate of the electrolyte passing through the magnetizer for providing the magnetic field gradient force is 100-fold and 150L/min, and the current density of the zinc electrodeposition process is 400-fold and 450A2The temperature is 30-35 ℃;
step 2: and (3) carrying out an electrodeposition experiment, taking out the residual anode and the cathode zinc after the electrodeposition experiment is finished, drying and weighing, and finally carrying out chemical component analysis on the dried cathode product, wherein the calculation formula is as follows:
wherein p is the power consumption, M is the mass of the deposited zinc, V is the cell voltage, f is the faraday constant, z is the valence state of the deposited ions, M is the atomic weight, and t is the electrodeposition time.
In the technical scheme of the method for optimizing the zinc electrodeposition process, the further preferable technical scheme is characterized in that:
1. the magnetic induction intensity of the Lorentz force generated in the step 1 is 1T, and the magnetic induction intensity of the magnetic field gradient force is 3T;
2. in the step 1, the flow rate of the electrolyte passing through the magnetizing device providing the Lorentz force is 200L/min, the flow rate of the electrolyte passing through the magnetizing device providing the magnetic field gradient force is 100L/min, and the current density in the zinc electrodeposition process is 420A/m2The temperature was 35 ℃.
Compared with the prior art, the invention can improve H+Over voltage, inhibition of hydrogen evolution, and reduction of Mn2+The oxidation reaction process achieves the purpose of protecting the anode and reduces Cu2+、Ni2+、Co2+The probability of discharge deposition at the cathode prevents the occurrence of the phenomenon of plate burning. Blocking of Fe2+、Fe3+A redox reaction occurs. Meanwhile, the generation of Ge hydride can be prevented, and the electric energy consumption is reduced. Promoting Ca2+And Mg2+With SO4 2-Salt bridges are not easy to form between the two, and consequently, the crystallization precipitation of calcium sulfate is further reduced, the probability of increasing the resistance of the calcium sulfate is reduced, the internal energy of a system is increased, and the resistance of electrolyte and the voltage drop of an electrodeposition tank are reduced.
Detailed Description
The following will clearly and completely describe the technical solutions in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Embodiment 1, a method for optimizing a zinc electrodeposition process, comprising the steps of, step 1: measuring Zn in electric liquid2+、H2SO4And the concentration of other impurity ions, the magnetizing device is connected to the liquid inlet pipe of the electrolytic cell, and the electrolyte passes through the head of the magnetizing deviceFirstly under the action of Lorentz force and then under the action of magnetic field gradient force, the magnetic induction intensity for generating the Lorentz force is 1-1.5T, the magnetic induction intensity for providing the magnetic field gradient force is 2-3T, when the electrolyte passes through the magnetic field for providing the Lorentz force, the pipeline adopts a flow dividing measure, namely 1 set of magnetic field for providing the Lorentz force needs to be matched with 2 sets of magnetic field for providing the magnetic field gradient force, the flow rate of the electrolyte passing through the magnetizing device for providing the Lorentz force is 120-fold-240L/min, the flow rate of the electrolyte passing through the magnetizing device for providing the magnetic field gradient force is 100-fold-150L/min, and the current density in the zinc electrodeposition process is 400-fold-450A/m2The temperature is 30-35 ℃; step 2: and (3) carrying out an electrodeposition experiment, taking out the residual anode and the cathode zinc after the electrodeposition experiment is finished, drying and weighing, and finally carrying out chemical component analysis on the dried cathode product, wherein the calculation formula is as follows:
wherein p is the power consumption, M is the mass of the deposited zinc, V is the cell voltage, f is the faraday constant, z is the valence state of the deposited ions, M is the atomic weight, and t is the electrodeposition time. The current density of the zinc electrodeposition process is 400-450A/m2The temperature is about 30-35 ℃, and the additive: 0.01-0.15g/L of bovine gelatin, 0.3-0.4g/L of strontium carbonate, and the weight ratio of anode: pb-0.3Ag polar plate. ρ (H)2SO4)/ρ(Zn2 +) 3-3.9, the interval is enlarged, and the adaptability of the zinc electrodeposition process is strong. The flow rate of the electrolyte passing through the magnetizing device providing Lorentz force is 1.2-1.5 times of that of the traditional zinc electrodeposition process, and the flow rate of the electrolyte passing through the magnetizing device providing magnetic field gradient force is equal to that of the traditional process. The invention firstly utilizes Lorentz force generated by a magnetic field to moderately thin Zn2+And the thickness of chemical hydration layer of other positive and negative ions, reduce the size of hydrone cluster; then the Zn is thinned again by utilizing the magnetic field gradient force generated by the magnetic field2+The thickness of the chemical hydration layer is reduced, the size of the hydrone cluster is reduced, and H is increased+、Mn2+、Cu2+、Fe2+、Fe3+、Ge4+、Ni2+、Co2+、Ca2+、Mg2+The thickness of the hydration layer of the paramagnetic ions is reduced to reduce the decomposition voltage and the resistance voltage of zinc sulfate and reduce the magnetic energy and the activity of the paramagnetic ions such as hydrogen, manganese, copper, iron, germanium, nickel, cobalt, calcium, magnesium and the like.
Example 2, the method for optimizing the zinc electrodeposition process according to example 1, wherein: the magnetic induction intensity of the Lorentz force generated in the step 1 is 1T, and the magnetic induction intensity of the magnetic field gradient force is 3T.
Example 3, the method for optimizing a zinc electrodeposition process according to example 1 or 2, wherein: in the step 1, the flow rate of the electrolyte passing through the magnetizing device providing the Lorentz force is 200L/min, the flow rate of the electrolyte passing through the magnetizing device providing the magnetic field gradient force is 100L/min, and the current density in the zinc electrodeposition process is 420A/m2The temperature was 35 ℃.
Example 4, the following table measured the ion concentrations in the electrowinning fluid:
(1) first, the magnetic induction intensity for providing the Lorentz force is set to 0T, and the magnetic induction intensity for providing the magnetic field gradient force is set to 0T. The flow rate of the electrolyte passing through the magnetizing device providing the Lorentz force is 200/min, and the flow rate of the electrolyte passing through the magnetizing device providing the magnetic field gradient force is 100L/min. The current density in the zinc electrodeposition process is 420A/m2About 35 ℃, additive: bovine glue 0.15g/L, strontium carbonate 0.4g/L, anode: a Pb-0.3Ag polar plate, and an Al plate as a cathode; (2) the steps are as follows
After the completion, the anode and the starting sheet are placed in an electrowinning cell, and the area S of the starting sheet entering the electrowinning cell is calculated3＝0.011m2The formula J according to the current density is current/S3Determine the magnitude of current to be 4.6A, cell voltage: 0.35V, and supplementing new liquid in the process to ensure the concentration of zinc sulfate; (3) after 24h of electrodeposition, the cell voltage is 3.57V, the current efficiency is 89%, and the cathode zinc appears on a sintered plate.
Example 5, (1) first, a lifter was providedThe magnetic induction intensity for Lorentz force is 1T, and the magnetic induction intensity for magnetic field gradient force is 3T; the flow rate of the electrolyte passing through the magnetizing device providing the Lorentz force is 200/min, and the flow rate of the electrolyte passing through the magnetizing device providing the magnetic field gradient force is 100L/min. The current density in the zinc electrodeposition process is 420A/m2About 35 ℃, additive: bovine glue 0.15g/L, strontium carbonate 0.4g/L, anode: a Pb-0.3Ag polar plate, and an Al plate as a cathode; (2) the steps are as follows
After the completion, the anode and the starting sheet are placed in an electrowinning cell, and the area S of the starting sheet entering the electrowinning cell is calculated3＝0.011m2The formula J according to the current density is current/S3Determine the magnitude of current to be 4.6A, cell voltage: 0.35V, and supplementing new liquid in the process to ensure the concentration of zinc sulfate; (3) after 24h of electrodeposition, the obtained cell voltage is 3.1V, the current efficiency is 98 percent, and the cathode zinc is very smooth.
Example 6, (1) first, the magnetic induction providing the lorentz force is set to 1T, and the magnetic induction providing the magnetic field gradient force is set to 0T; the flow rate of the electrolyte passing through the magnetizing device providing the Lorentz force is 200/min, and the flow rate of the electrolyte passing through the magnetizing device providing the magnetic field gradient force is 100L/min. The current density in the zinc electrodeposition process is 420A/m2About 35 ℃, additive: bovine glue 0.15g/L, strontium carbonate 0.4g/L, anode: a Pb-0.3Ag polar plate, and an Al plate as a cathode; (2) the steps are as follows
After the completion, the anode and the starting sheet are placed in an electrowinning cell, and the area S of the starting sheet entering the electrowinning cell is calculated3＝0.011m2The formula J according to the current density is current/S3Determine the magnitude of current to be 4.6A, cell voltage: 0.35V, and supplementing new liquid in the process to ensure the concentration of zinc sulfate; (3) after 24h of electrodeposition, the obtained cell voltage is 3.43V, the current efficiency is 92 percent, and the cathode zinc is rough.
The above description is only for the preferred embodiments of the present invention, but the protection scope of the present invention is not limited thereto, and any person skilled in the art can substitute or change the technical solution of the present invention and the inventive concept thereof within the scope of the present invention.
Claims (3)
1. A method for optimizing a zinc electrodeposition process is characterized by comprising the following steps:
step 1: measuring Zn in electric liquid2+、H2SO4And the concentration of other impurity ions, connecting the magnetizer to the liquid inlet pipe of the electrolytic bath, leading the electrolyte to be firstly acted by Lorentz force through the magnetizer and then acted by magnetic field gradient force, wherein the magnetic induction intensity for generating the Lorentz force is 1-1.5T, the magnetic induction intensity for providing the magnetic field gradient force is 2-3T, when the electrolyte passes through the magnetic field for providing the Lorentz force, a pipeline adopts a flow dividing measure, namely 1 set of magnetic field for providing the Lorentz force needs to be matched with 2 sets of magnetic field for providing the magnetic field gradient force, the flow rate of the electrolyte passing through the magnetizer for providing the Lorentz force is 120-fold and 240L/min, the flow rate of the electrolyte passing through the magnetizer for providing the magnetic field gradient force is 100-fold and 150L/min, and the current density of the zinc electrodeposition process is 400-fold and 450A2The temperature is 30-35 ℃;
step 2: and (3) carrying out an electrodeposition experiment, taking out the residual anode and the cathode zinc after the electrodeposition experiment is finished, drying and weighing, and finally carrying out chemical component analysis on the dried cathode product, wherein the calculation formula is as follows:
wherein p is the power consumption, M is the mass of the deposited zinc, V is the cell voltage, f is the faraday constant, z is the valence state of the deposited ions, M is the atomic weight, and t is the electrodeposition time.
2. The method of optimizing a zinc electrodeposition process according to claim 1, wherein: the magnetic induction intensity of the Lorentz force generated in the step 1 is 1T, and the magnetic induction intensity of the magnetic field gradient force is 3T.
3. The method of optimizing a zinc electrodeposition process according to claim 1, wherein: in the step 1, the flow rate of the electrolyte passing through the magnetizing device providing the Lorentz force is 200L/min, the flow rate of the electrolyte passing through the magnetizing device providing the magnetic field gradient force is 100L/min, and the current density in the zinc electrodeposition process is 420A/m2The temperature was 35 ℃.
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