阅读说明：本技术 一种用超声波净化硫酸锌溶液的方法及装置 (Method and device for purifying zinc sulfate solution by using ultrasonic waves ) 是由 李永佳 雷霆 杨志鸿 刘捷 于 2020-07-13 设计创作，主要内容包括：本发明公开了一种用超声波净化硫酸锌溶液的方法及装置,该方法过程：硫酸锌溶液依次经过一段净化、二段净化、三段净化,在三个净化阶段的过程中用超声波射入溶液。净化过程中利用超声波对硫酸锌溶液进行超声波照射,使超声波射入硫酸锌溶液,在溶液中产生超声空化效应,伴随产生的高速射流去除硫酸锌溶液中包裹在锌粉表面的钝化膜,使锌粉始终保持新鲜的活性表面,从而强化锌粉置换反应的作用过程。本发明方法用超声波改善净化效果,可明显降低锌粉用量、提高置换反应效率、降低溶液中杂质含量和降低湿法炼锌的生产成本。(The invention discloses a method and a device for purifying zinc sulfate solution by using ultrasonic waves, wherein the method comprises the following steps: the zinc sulfate solution is subjected to first-stage purification, second-stage purification and third-stage purification in sequence, and ultrasonic waves are injected into the solution in the three purification stages. The ultrasonic irradiation is carried out on the zinc sulfate solution by utilizing ultrasonic waves in the purification process, the ultrasonic waves are irradiated into the zinc sulfate solution to generate an ultrasonic cavitation effect in the solution, a passivation film coated on the surface of the zinc powder in the zinc sulfate solution is removed by high-speed jet flow generated along with the ultrasonic cavitation effect, the zinc powder is enabled to be kept on a fresh active surface all the time, and therefore the action process of zinc powder replacement reaction is strengthened. The method of the invention uses ultrasonic waves to improve the purification effect, can obviously reduce the using amount of zinc powder, improve the replacement reaction efficiency, reduce the impurity content in the solution and reduce the production cost of zinc hydrometallurgy.)

1. The method for purifying the zinc sulfate solution by using ultrasonic waves is characterized in that the zinc sulfate solution sequentially undergoes first-stage purification, second-stage purification and third-stage purification, and the solution is injected by using the ultrasonic waves in the process of the three purification stages, and the method comprises the following specific steps:

step 1, first-stage purification; heating the zinc sulfate solution to 60-80 ℃ by using a heat exchanger, adding zinc powder into a size mixing tank to mix with the zinc sulfate solution, then sending the mixed zinc sulfate solution into a first section of purification tank by using a delivery pump, and starting an ultrasonic generator to react in the first section of purification tank for 20 min;

step 2, second-stage purification; conveying the first-stage purified liquid into a second-stage purifying tank by a conveying pump, controlling the temperature at 60-80 ℃, adding zinc powder, copper sulfate and antimony white powder, and starting an ultrasonic generator to react in the second-stage purifying tank for 20 min;

step 3, three-stage purification; conveying the second-stage purified liquid into a third-stage purifying tank by a conveying pump, controlling the temperature at 60-80 ℃, adding zinc powder, starting an ultrasonic generator to react in the third-stage purifying tank for 20min to obtain purified liquid;

wherein, one section purification groove, two-stage process purification groove, three-section purification groove structure are the same, and supersonic generator installs in purifying the inslot, and the frequency of ultrasonic wave is 20 ~ 50kHz, and the sound intensity is 200 ~ 800w/cm²The action period is 5min, the ultrasonic wave is started for 4min and stopped for 1min, and the reciprocating circulation is carried out.

2. The method for purifying zinc sulfate solution by using ultrasonic waves as claimed in claim 1, characterized in that: the concentration of copper ions in the zinc sulfate solution is less than 150mg/L, the concentration of cadmium ions is less than 1000mg/L, the concentration of nickel ions is less than 100mg/L, the concentration of cobalt ions is 100mg/L, other impurities reach the standard, and the pH value is 3-5.

3. The method for purifying zinc sulfate solution by using ultrasonic waves as claimed in claim 1, characterized in that: in the step 1, the adding amount of the zinc powder is 1.2-1.4 times of the content of impurity Cu + Cd in the zinc sulfate solution.

4. The method for purifying zinc sulfate solution by using ultrasonic waves as claimed in claim 1, characterized in that: in the step 2, the dosage of the zinc powder is 30-50 times of the content of Co + Ni impurities in the solution after Cu and Cd are removed, the dosage of the copper sulfate is 20mg/L, and the dosage of the antimony white powder is 5 mg/L.

5. The method for purifying zinc sulfate solution by using ultrasonic waves as claimed in claim 1, characterized in that: in the step 3, the using amount of the zinc powder is 0.6-1.5 g/L.

6. The utility model provides a device with ultrasonic purification zinc sulfate solution which characterized in that: the device is for purifying the groove, purifies the groove and includes cell body, capping, supersonic generator, transmission, (mixing) shaft, stirring paddle leaf, the cell body is equipped with the cavity, and the capping is used for shutoff concave cavity mouth, the cell body lateral wall is equipped with inlet, drain, liquid outlet, (mixing) shaft one end is connected with transmission, and the other end passes the capping middle part and stretches into in the cavity, stirring paddle leaf installs on the (mixing) shaft, supersonic generator is one at least, sets up on the inner wall of cell body, and supersonic generator is connected with the ultrasonic power electricity.

7. The device for purifying zinc sulfate solution by using ultrasonic waves of claim 6 is characterized in that: the liquid inlet and the vent are arranged on the same vertical direction, the liquid inlet is arranged on the upper portion, the vent is arranged on the lower portion, and the liquid outlet is arranged on the side wall opposite to the liquid inlet.

8. The device for purifying zinc sulfate solution by using ultrasonic waves of claim 7 is characterized in that: the liquid outlet device is characterized in that a communicating channel is arranged in the tank body, the communicating channel is vertically arranged and is tightly attached to the inner wall of the tank body, one end of the communicating channel is connected with the liquid outlet, and the other end of the communicating channel extends into the bottom of the tank body and is provided with a liquid outlet hole.

Technical Field

The invention belongs to the technical field of purification of zinc sulfate solution in zinc hydrometallurgy, and particularly relates to a method and a device for purifying zinc sulfate solution by using ultrasonic waves.

Background

The metal zinc has good rolling, wear resistance and corrosion resistance, can be made into an alloy with better performance with various metals, the consumption of the zinc is inferior to that of copper and aluminum, and the zinc is mainly used for galvanizing (46%), manufacturing copper alloy (15%), manufacturing zinc alloy (15%), oxidizing zinc products (11%), manufacturing batteries (13%) and the like.

Zinc is mainly prepared by a wet method, and with increasing shortage of zinc metal resources and increasing of zinc consumption, how to reduce the cost of zinc hydrometallurgy and secondary utilization of zinc metal are particularly important.

The zinc leachate is an intermediate raw material for producing electrolytic zinc, and contains a large amount of impurities, such as: cu, Cd, Ni, Co, Ge, Sb, etc., which greatly affect the current efficiency of the subsequent electrolytic process and the quality of electrolytic zinc. In order to remove these impurities, a large amount of high-quality zinc powder is used in the purification process, and since the consumption of the zinc powder accounts for about 20% of the processing cost of zinc metallurgy and the actual consumption of the zinc powder is 10 times to 100 times of the theoretical consumption, the activity of the zinc powder is maintained, and the consumption of the zinc powder is reduced, which plays an important role in zinc metallurgy.

In the zinc calcine leaching solution, the impurities mainly comprise two types, wherein the first type is impurities which influence the product quality, such As Fe, Cu and Cd, and the second type is impurities which influence the electrodeposition process, such As As, Sb, Ni, Co, Ge, F, Cl and the like. Fe in the first class of impurities is removed by adjusting the pH value of a solution for hydrolysis at the last stage of leaching, and for Cu and Cd, electric furnace zinc powder is generally adopted for displacement precipitation removal, and the operation is completed at the first stage of purification; as, Sb, Ge and In the second impurities are hydrolyzed and adsorbed together with the neutralization and hydrolysis of Fe to be removed, Ni and Co which are difficult to hydrolyze remain In the solution, particularly Co is difficult to remove, and In order to remove Ni and Co In the solution As much As possible, an antimonate purification process is mostly adopted, under the condition that zinc powder is used As a reducing agent, antimonate (comprising antimony compounds such As potassium antimonate and antimony white) is used for removing nickel and cobalt, and the operation is finished In the second stage of purification.

The cobalt removing process of antimonate is to make zinc powder produce displacement reaction to lower the potential of zinc sulfate solution and maintain the potential in negative potential area, so that cobalt ion and antimonate react to produce CoSb compound. CoSb is stable when the activity and amount of zinc powder are enough to maintain a low potential region (-1.0 to-0.5V), and redissolved when the zinc powder replacement reaction is not enough to maintain a low potential region, and a large amount of zinc powder needs to be supplemented in order to prevent redissolution of CoSb. The usage of the zinc powder in the process of removing Ni and Co accounts for more than 80 percent of the total consumption of the zinc powder, and the usage of the zinc powder in the process of removing Co accounts for about 60 percent of the total usage of the zinc powder. Therefore, how to improve the activity of the zinc powder is important for saving energy and reducing consumption in the purification process of the zinc sulfate solution.

Research shows that after entering a zinc sulfate solution, zinc powder particles contact with Ni and Co ions in the solution to generate a replacement reaction on the surfaces of the zinc powder particles, replaced impurities such as metal nickel, cobalt and the like are remained on the surfaces of the zinc powder particles in a solid state, and along with the replacement reaction, the whole surfaces of the zinc powder particles are completely covered by Ni and Co, so that the wrapped internal zinc powder cannot be effectively utilized, and the zinc powder is large in consumption and high in cost.

Meanwhile, the replacement reaction of the zinc powder reduces hydrogen ions in the solution into hydrogen, the pH value of the solution tends to rise, basic zinc salt (including Zn (OH)2) is promoted to generate, and a passivation film is formed on the surface of the zinc powder, so that the zinc powder is reduced or inactivated. In order to weaken or eliminate the negative effect of the basic zinc salt passivation film, the nickel-cobalt removing process of the antimonate needs to adopt high-strength mechanical stirring, the pH is controlled to be 3-5, the temperature is controlled to be 75-85 ℃, but the actual consumption of the zinc powder is still 100-200 times of the theoretical consumption and accounts for 3-5% of the yield of the electrozinc.

After the second stage of purification is finished, in order to remove the redissolved impurities, the third stage of purification is adopted, and zinc powder is continuously added for replacement and impurity removal. High-quality zinc powder is required to be added in the three stages of the purification of the zinc sulfate solution, so that the zinc powder keeps activity and the efficiency of replacement reaction is improved in the purification process of the zinc sulfate solution, which is always a key technology for the research and the breakthrough of the zinc hydrometallurgy industry.

Aiming at the zinc sulfate solution purification process, the invention develops a method and a device for purifying the zinc sulfate solution by using ultrasonic waves on the basis of a large number of experiments, and aims to improve the activity of zinc powder in the solution, improve the replacement reaction efficiency, reduce the impurity content in the solution, reduce the production cost of zinc hydrometallurgy and the like.

Disclosure of Invention

The invention provides a method and a device for purifying zinc sulfate solution by ultrasonic wave, aiming at the problems that zinc powder is commonly used to replace impurities in the solution in the existing zinc sulfate solution purification process, the impurities are deposited on the surface of the zinc powder after being replaced, so that the surface of the zinc powder is covered by all or most of impurity elements, the activity of the zinc powder is greatly reduced until the zinc powder is completely ineffective, the purification efficiency is low, the zinc powder consumption is large, the replaced impurities are impure and the like,

in order to solve the technical problems, the invention adopts the technical scheme that:

a method for purifying zinc sulfate solution by using ultrasonic waves comprises the steps of sequentially carrying out first-stage purification, second-stage purification and third-stage purification on the zinc sulfate solution, and injecting the ultrasonic waves into the solution in the process of the three purification stages. The ultrasonic wave is introduced in the whole zinc sulfate solution purification process, the mechanical, thermal, optical, electrical and chemical effects of the ultrasonic wave are utilized to fully disperse the additives in the purification process, the purification process is efficiently completed, the replaced impurities fall off from the surface of the zinc powder, and the zinc powder is enabled to keep activity all the time. The method comprises the following specific steps:

step 1, first-stage purification; heating the zinc sulfate solution to 60-80 ℃ by using a heat exchanger, adding zinc powder into a size mixing tank to mix with the zinc sulfate solution, then sending the mixed zinc sulfate solution into a first section of purification tank by using a delivery pump, and starting an ultrasonic generator to react in the first section of purification tank for 20 min;

step 2, second-stage purification; conveying the first-stage purified liquid into a second-stage purifying tank by a conveying pump, controlling the temperature at 60-80 ℃, adding zinc powder, copper sulfate and antimony white powder, and starting an ultrasonic generator to react in the second-stage purifying tank for 20 min;

step 3, three-stage purification; conveying the second-stage purified liquid into a third-stage purifying tank by a conveying pump, controlling the temperature at 60-80 ℃, adding zinc powder, starting an ultrasonic generator to react in the third-stage purifying tank for 20min to obtain purified liquid;

wherein, the first section purification tank, the second section purification tank and the third section purification tank are structurally mutually connectedMeanwhile, the ultrasonic generator is arranged in the purifying tank, the frequency of the ultrasonic is 20-50 kHz, and the sound intensity is 200-800 w/cm²The action period is 5min, the ultrasonic wave is started for 4min and stopped for 1min, and the reciprocating circulation is carried out.

Further, the concentration of copper ions in the zinc sulfate solution is less than 150mg/L, the concentration of cadmium ions is less than 1000mg/L, the concentration of nickel ions is less than 100mg/L, the concentration of cobalt ions is 100mg/L, other impurities reach the standard, and the pH value is 3-5.

Further, in the step 1, the adding amount of the zinc powder is 1.2-1.4 times of the content of the impurity Cu + Cd in the zinc sulfate solution.

Furthermore, in the step 2, the dosage of the zinc powder is 30-50 times of the content of Co + Ni impurities in the solution after Cu and Cd are removed, the dosage of the copper sulfate is 20mg/L, and the dosage of the antimony white powder is 5 mg/L.

Furthermore, in the step 3, the using amount of the zinc powder is 0.6-1.5 g/L.

The ultrasonic irradiation is carried out on the zinc sulfate solution by utilizing ultrasonic waves in the purification process, the ultrasonic waves are irradiated into the zinc sulfate solution to generate an ultrasonic cavitation effect in the solution, a passivation film coated on the surface of the zinc powder in the zinc sulfate solution is removed by high-speed jet flow generated along with the ultrasonic cavitation effect, the zinc powder is enabled to be kept on a fresh active surface all the time, and therefore the action process of zinc powder replacement reaction is strengthened. Meanwhile, the impurity crystal grains are vibrated and cleaned by ultrasonic waves, so that the impurity crystal grains always keep fresh active surfaces, the crystallization effect among the crystal grains is strengthened, the generation reaction of an impurity intermetallic compound is further promoted, and the purification process is accelerated.

The utility model provides a device with ultrasonic purification zinc sulphate solution, the device is for purifying the groove, purifies the groove and includes cell body, capping, supersonic generator, transmission, (mixing) shaft, stirring paddle leaf, the cell body is equipped with the cavity, and the capping is used for shutoff cavity mouth, the cell lateral wall is equipped with inlet, drain, liquid outlet, (mixing) shaft one end is connected with transmission, and the other end passes the capping middle part and stretches into in the cavity, stirring paddle leaf installs on the (mixing) shaft, supersonic generator is one at least, sets up on the inner wall of cell body, and supersonic generator is connected with the ultrasonic power electricity.

Furthermore, the liquid inlet and the vent are arranged on the same vertical direction, the liquid inlet is arranged on the upper portion, the vent is arranged on the lower portion, and the liquid outlet is arranged on the side wall opposite to the liquid inlet.

Furthermore, a communicating channel is arranged in the tank body, the communicating channel is vertically arranged and is tightly attached to the inner wall of the tank body, one end of the communicating channel is connected with the liquid outlet, and the other end of the communicating channel extends into the bottom of the tank body and is provided with a liquid outlet hole.

The technical principle of the invention is as follows: introducing into a purifying tank filled with zinc sulfate solution, wherein the introduction frequency is 20-50 kHz, and the sound intensity is 200-800 w/cm²Under the condition that the ultrasonic emitter and the stirring device operate together, the pH value and the temperature of the solution and the addition of zinc powder and other substances are well controlled, and impurities in the solution are purified under the combined action of the ultrasonic and the additives. Ultrasonic waves are injected into the zinc sulfate solution to generate an ultrasonic cavitation effect in the solution and generate high-speed jet flow along with the ultrasonic cavitation effect, so that a passive film on the surface of the zinc powder is effectively removed, the zinc powder always keeps a fresh active surface, and the zinc powder effectively participates in a replacement reaction process. In the second purification stage of adding zinc powder and antimonite to remove nickel and cobalt, the zinc powder activated by ultrasonic wave can be quickly reduced and stably maintain the solution potential in a more negative potential area, so that the CoSb generation reaction is greatly accelerated, and after the ultrasonic wave acts for 30-50 minutes, the nickel and cobalt concentrations in the purified solution reach the quality requirement of zinc electrolyte, thereby realizing the improvement of the zinc sulfate solution purification effect by the ultrasonic wave.

After the technical scheme is adopted, compared with the prior art, the invention has the following beneficial effects.

The invention utilizes ultrasonic waves to improve the environmental condition of zinc sulfate solution, uses the ultrasonic waves to irradiate the solution in the whole purification process, and utilizes the mechanical, thermal, optical, electrical and chemical effects of the ultrasonic waves to fully disperse additives in the purification process, so that the purification process is efficiently completed, the replaced impurities fall off from the surface of the zinc powder, and the zinc powder keeps activity and the like all the time.

The following describes embodiments of the present invention in further detail with reference to the accompanying drawings.

Drawings

The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this application, illustrate embodiment(s) of the invention and together with the description serve to explain the invention without limiting the invention to its proper form. It is obvious that the drawings in the following description are only some embodiments, and that for a person skilled in the art, other drawings can be derived from them without inventive effort. In the drawings:

FIG. 1 is a schematic view showing the structure of a purification tank according to the present invention;

in the figure: 1-a transmission device; 2-a gearbox; 3-a vent hole; 4-ultrasonic power supply; 5-a groove cover; 6-liquid inlet; 7-a trough body; 8-an ultrasonic generator; 9-a vent; 10-a stirring shaft; 11-stirring blade; 12-a liquid outlet; 13-liquid outlet.

It should be noted that the drawings and the description are not intended to limit the scope of the inventive concept in any way, but to illustrate it by a person skilled in the art with reference to specific embodiments.

Detailed Description

In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and the following embodiments are used for illustrating the present invention and are not intended to limit the scope of the present invention.