CN115652373A - Purification method for removing cadmium from zinc sulfate electrolyte by using zinc powder assisted by ultrasonic waves/copper ions - Google Patents
Purification method for removing cadmium from zinc sulfate electrolyte by using zinc powder assisted by ultrasonic waves/copper ions Download PDFInfo
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- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 title claims abstract description 140
- 229910000368 zinc sulfate Inorganic materials 0.000 title claims abstract description 140
- 229960001763 zinc sulfate Drugs 0.000 title claims abstract description 140
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 121
- 239000003792 electrolyte Substances 0.000 title claims abstract description 117
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 229910001431 copper ion Inorganic materials 0.000 title claims abstract description 46
- 229910052793 cadmium Inorganic materials 0.000 title claims abstract description 44
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 238000000034 method Methods 0.000 title claims abstract description 42
- 238000000746 purification Methods 0.000 title claims abstract description 27
- WLZRMCYVCSSEQC-UHFFFAOYSA-N cadmium(2+) Chemical compound [Cd+2] WLZRMCYVCSSEQC-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000007788 liquid Substances 0.000 claims abstract description 36
- 239000002893 slag Substances 0.000 claims abstract description 23
- 238000001035 drying Methods 0.000 claims abstract description 11
- 238000000227 grinding Methods 0.000 claims abstract description 11
- 238000000926 separation method Methods 0.000 claims abstract description 11
- 229910000365 copper sulfate Inorganic materials 0.000 claims abstract description 10
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims abstract description 10
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 7
- 239000011701 zinc Substances 0.000 abstract description 32
- 229910052725 zinc Inorganic materials 0.000 abstract description 26
- 230000000694 effects Effects 0.000 abstract description 15
- 230000008859 change Effects 0.000 abstract description 5
- 239000010949 copper Substances 0.000 abstract description 5
- 238000009854 hydrometallurgy Methods 0.000 abstract description 3
- 230000009471 action Effects 0.000 abstract description 2
- 238000002604 ultrasonography Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 46
- 230000000052 comparative effect Effects 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 13
- 239000003638 chemical reducing agent Substances 0.000 description 10
- 239000012535 impurity Substances 0.000 description 10
- 230000008569 process Effects 0.000 description 10
- 150000002500 ions Chemical class 0.000 description 9
- 238000003756 stirring Methods 0.000 description 8
- 238000004070 electrodeposition Methods 0.000 description 6
- 239000010410 layer Substances 0.000 description 6
- 238000002386 leaching Methods 0.000 description 6
- 239000002184 metal Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 238000005054 agglomeration Methods 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000011247 coating layer Substances 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 238000006073 displacement reaction Methods 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000008364 bulk solution Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005363 electrowinning Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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Abstract
The invention relates to a purification method for removing cadmium from zinc sulfate electrolyte by zinc powder under the assistance of ultrasonic waves/copper ions, belonging to the technical field of zinc hydrometallurgy purification slag treatment. Adding copper sulfate into zinc sulfate electrolyte containing cadmium ions, and adjusting the concentration of copper sulfate in the zinc sulfate electrolyte to 300-700g/L to obtain pretreated zinc sulfate electrolyte; adding zinc powder into the pretreated zinc sulfate electrolyte, performing ultrasonic enhanced replacement for 40-60min, performing solid-liquid separation to obtain purified slag and zinc sulfate electrolytic purified liquid, drying the purified slag, and grinding. Mechanical and cavitation effects using ultrasound, cu 2+ The electropositive reinforced zinc powder removes Cd from the zinc sulfate electrolyte 2+ Intensity of ultrasonic wavesUnder the action of Cu 2+ Can promote the potential of zinc sulfate solution to change to the positive direction, increase the potential difference between zinc and cadmium, improve the thermodynamic power of cadmium replaced by zinc powder, and improve Cd 2+ The removal rate of (3).
Description
Technical Field
The invention relates to a purification method for removing cadmium from zinc sulfate electrolyte by using ultrasonic waves/copper ions to assist zinc powder, belonging to the technical field of zinc hydrometallurgy.
Background
The zinc hydrometallurgy is taken as the main flow process of zinc smelting development to bear more than 80 percent of refined zinc production in the world. The zinc calcine generated after the zinc concentrate is roasted is leached, so that zinc in the calcine enters a leaching solution in the form of ions, then impurity ions in the leaching solution are removed through purification, then the obtained electro-deposition solution is electrodeposited to obtain metal zinc, finally zinc sulfate solution obtained through neutral leaching of zinc ingot zinc roasted ore formed through fusion casting contains more impurities, the content of the impurities exceeds a certain degree, and adverse effects are brought to the zinc electrodeposition process, the existence of the impurity ions not only affects the quality of the metal zinc, but also can remarkably reduce the current efficiency and increase the electricity consumption, and is very harmful to the zinc electrodeposition process. Therefore, the zinc sulfate solution must be purified before electrodeposition, and harmful impurities in the zinc sulfate solution are removed to meet the requirement of zinc electrowinning so as to ensure that high-purity cathode zinc is obtained during electrodeposition. The purification process aims to remove harmful impurity ions in the zinc sulfate solution, improve the quality of the electrolyte and comprehensively recover valuable metals. The quality of the purification effect directly affects the quality of the zinc product and the economic benefit of the electrodeposition. The method for purifying zinc sulfate solution is mainly divided into two types of organic reagent purification method and zinc powder replacement method, and the zinc powder replacement method is the most commonly used method at present.
In the process of purifying the zinc powder, the unit consumption of the zinc powder is high due to the agglomeration of the zinc powder caused by poor mass transfer. In the process of zinc powder replacement, zinc loses electrons, and Zn is generated around the zinc powder 2+ The mass transfer coefficient of zinc is smaller than that of hydrogen, so that Zn surrounds the zinc powder 2+ Concentration ratio of Zn in bulk solution 2+ High concentrations produce local charge imbalances. Based on the charge concentration effect, negative ions SO 4 2- And OH - Will be accumulated in Zn 2+ Around, form bilayer structure, prevent impurity ion (especially the ion with positive charge) to zinc powder surface transmission, hinder the emergence of replacement reaction, make zinc powder in zinc sulfate solution diffusion effect not good to lead to zinc powder to appear reunion phenomenon. The agglomeration of the zinc powder reduces the surface area and the amount of reactive zinc powder. When zinc powder reacts in zinc sulfate solution, impurity ions are generated on the surface of the zinc powderAnd (4) generating a replacement product through the replacement reaction, and gathering the replacement product on the surface of the zinc powder to generate a replacement product coating layer to hinder replacement. In addition, in the process of replacing and purifying the zinc sulfate solution by the zinc powder, the pH value is generally maintained at about 4-5, but due to the occurrence of hydrogen evolution reaction, the acid and alkali on the local part of the surface of the zinc powder are unbalanced, and the local pH value on the surface of the zinc powder is increased by 2-3 compared with the overall pH value. Zn 2+ Hydrolyzing on the surface of the zinc powder to form a basic zinc salt wrapping layer, wherein the wrapping layer covers the surface of the zinc powder. The existence of parcel layer makes the area that exposes of zinc powder reduce, has reduced the chance of impurity ion and zinc powder contact, prevents that the inlayer zinc powder from continuing to carry out these several kinds of phenomena of replacement reaction and all can prevent Cd (II) and zinc powder to combine to lead to the bulk consumption of zinc powder.
In summary, the agglomeration and the wrapping problem cause the zinc powder purification method to consume relatively large amount of zinc powder and slow replacement speed in practical situations, so a purification method capable of reducing the amount of zinc powder and accelerating the purification speed is needed.
Disclosure of Invention
The invention provides a purification method for removing cadmium from zinc sulfate electrolyte by using ultrasonic waves/copper ions, aiming at the problems of serious zinc powder agglomeration and coating, high treatment cost, high zinc powder consumption, long treatment period, high energy consumption and the like in the cadmium removal of zinc powder from zinc sulfate electrolyte, and the method adopts the mechanical effect and cavitation effect of the ultrasonic waves and the Cu effect 2+ The electropositive reinforced zinc powder removes Cd from the zinc sulfate electrolyte 2+ Under the action of ultrasonic wave reinforcement, cu 2+ Can promote the potential of the zinc sulfate solution to change to the positive direction, increase the potential difference between zinc and cadmium, improve the thermodynamic power of the zinc powder for replacing cadmium, and improve Cd 2+ The removal rate of (d); cavitation and mechanical effect generated by ultrasonic waves are beneficial to stripping a coating layer on the surface of the zinc powder, a special physical environment with local high temperature and high pressure is provided for the replacement reaction, the reaction rate is accelerated, the using amount of the zinc powder and the time required by the leaching process are greatly reduced, the production cost is reduced, and the operation is simple; the cadmium is precipitated into the solution by a zinc powder displacement cadmium method, so that the recovery of the metal cadmium is facilitated.
The invention solves the technical problems that the zinc powder wrapping layer is serious in the traditional cadmium replacement process by the zinc powder, so that the utilization rate of the zinc powder is low, and the purification cost is greatly increased; the zinc powder coating layer is timely stripped through the strengthening treatment of ultrasonic waves/copper ions, and the potential of the solution is promoted to change towards the positive direction, so that the removal rate of cadmium is greatly improved.
A method for removing cadmium from zinc sulfate electrolyte by using zinc powder assisted by ultrasonic waves/copper ions comprises the following steps:
(1) Adding copper sulfate into zinc sulfate electrolyte containing cadmium ions, and adjusting the concentration of copper ions in the zinc sulfate electrolyte to be 300-700mg/L to obtain pretreated zinc sulfate electrolyte;
(2) Adding zinc powder into the pretreated zinc sulfate electrolyte, performing ultrasonic enhanced replacement for 40-60min, performing solid-liquid separation to obtain purified slag and zinc sulfate electrolytic purified liquid, drying the purified slag, and grinding.
The concentration of zinc ions in the zinc sulfate electrolyte in the step (1) is 120-130g/L, and the concentration of cadmium ions is 1500-2000mg/L.
The pH value of the zinc sulfate electrolyte in the step (1) is 4-5.
The solid-to-liquid ratio g: mL of the zinc powder in the step (2) to the pretreated zinc sulfate electrolyte is 2-3.
The ultrasonic power density in the step (2) is 160-240W/L, and the ultrasonic frequency is 19.63-19.73kHz.
The replacement temperature in the step (2) is 40-60 ℃.
The purification principle of cadmium removal from zinc sulfate electrolyte by zinc powder assisted by ultrasonic waves/copper ions is as follows: the zinc with electronegativity is utilized to reduce cadmium ions with electronegativity more positive than zinc from the zinc sulfate solution, the standard potentials of zinc, cadmium and copper are-0.763 mV, -0.403mV and 0.344mV respectively, the positive standard potential copper is utilized to promote the potential of the solution to change towards the positive direction, so that the standard potential difference between zinc and cadmium is increased, and the thermodynamic driving force of the reaction is improved; the method has the advantages that the ultrasonic/copper ions and the zinc powder are subjected to synergistic effect, the mass transfer and displacement capacity of the zinc powder is improved by utilizing the ultrasonic cavitation and mechanical effects, the direct reaction rate of minerals and the oxidation process of an intermediate product are further improved, the inclusion on the surface of the zinc powder can be dissociated by ultrasonic waves, and the unreacted zinc powder is exposed to a zinc sulfate solution, so that the zinc powder and Cd (II) are fully reacted.
The beneficial effects of the invention are:
(1) According to the invention, zinc powder is used as a reducing agent, and the cadmium is removed from the zinc sulfate electrolyte by the aid of the ultrasonic waves/copper ions, compared with the traditional zinc powder replacement method, the cadmium replacement method has the advantages of high cadmium leaching efficiency, short leaching time and less zinc powder consumption by the aid of the ultrasonic waves/copper ions in cooperation with the zinc powder replacement;
(2) The invention utilizes the mechanical effect and the cavitation effect generated when the solution is treated by ultrasonic; in the process of crushing the cavitation bubbles, a reaction zone consisting of a soluble metal layer is also crushed to generate an acoustic flow effect and disturb the original steady diffusion, so that the cadmium removal rate is improved; the micro-jet generated by ultrasonic waves enables a wrapping layer on the surface of zinc powder to fall off, the acoustic cavitation provides a special local high-temperature and high-pressure material flow environment for the replacement reaction, the positive standard potential copper is utilized to promote the potential of the solution to change towards the positive direction, so that the standard potential difference between zinc and cadmium is increased, the thermodynamic driving force of the reaction is improved, and the removal rate of cadmium is improved; the mechanical effect generates the effect of mechanical stirring, promotes the contact of solid and liquid phases, is beneficial to the chemical reaction of an interface and improves the cadmium removal efficiency;
(3) The invention takes zinc powder as a reducing agent without impurities and produces Zn by reaction 2+ The zinc sulfate solution is not affected.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments, but the scope of the present invention is not limited to the description.
Comparative example 1: the cadmium ion concentration of the zinc sulfate electrolyte is shown in a table 1, and the purification method for removing cadmium from the zinc sulfate electrolyte by using zinc powder comprises the following specific steps:
TABLE 1 Zinc sulfate electrolyte cadmium ion concentration
| Element(s) | Cd |
| Concentration (mg/L) | 2000 |
Adding zinc powder (less than 200 meshes) as a reducing agent into zinc sulfate electrolyte containing cadmium ions, replacing for 40min at the temperature of 55 ℃ and the stirring speed of 350rpm, performing solid-liquid separation to obtain purified slag and zinc sulfate electrolyte purified liquid, drying the purified slag, grinding, and detecting the concentration of cadmium ions in the zinc sulfate electrolyte purified liquid; wherein the pH value of the zinc sulfate electrolyte is 4, the concentration of zinc ions is 120g/L, and the solid-to-liquid ratio g: mL of zinc powder to zinc sulfate solution is 3;
the concentration of cadmium ions in the zinc sulfate electrolyte purifying solution of the comparative example is 622.2mg/L.
Comparative example 2: the zinc sulfate electrolyte was the same as comparative example 1; the purification method for removing cadmium from zinc sulfate electrolyte by using zinc powder comprises the following specific steps:
(1) Adding copper sulfate into zinc sulfate electrolyte containing cadmium ions, and adjusting the concentration of copper ions in the zinc sulfate electrolyte to 300mg/L to obtain pretreated zinc sulfate electrolyte; wherein the pH value of the zinc sulfate electrolyte is 4, and the concentration of zinc ions is 120g/L;
(2) Adding zinc powder (less than 200 meshes) as a reducing agent into the pretreated zinc sulfate electrolyte, replacing for 40min at 55 ℃ and a stirring speed of 350rpm, performing solid-liquid separation to obtain purified slag and zinc sulfate electrolyte purified liquid, drying the purified slag, grinding, and detecting the concentration of cadmium ions in the zinc sulfate electrolyte purified liquid; wherein the solid-to-liquid ratio g: mL of the zinc powder to the zinc sulfate solution is 3;
the concentration of cadmium ions in the zinc sulfate electrolyte purifying solution of the comparative example is 530.3mg/L, and the concentration of copper ions in the zinc sulfate electrolyte purifying solution of the comparative example is 3.1mg/L.
Comparative example 3: the zinc sulfate electrolyte was the same as comparative example 1; the purification method for removing cadmium from zinc sulfate electrolyte by using zinc powder comprises the following specific steps:
adding zinc powder (smaller than 200 meshes) serving as a reducing agent into zinc sulfate electrolyte containing cadmium ions, performing ultrasonic wave enhanced replacement for 40min at the temperature of 55 ℃ and the stirring speed of 350rpm, performing solid-liquid separation to obtain purified slag and zinc sulfate electrolyte purified liquid, drying the purified slag, grinding, and detecting the concentration of the cadmium ions in the zinc sulfate electrolyte purified liquid; wherein the ultrasonic power density is 200W/L, the ultrasonic frequency is 19.63kHz, the pH value of the zinc sulfate electrolyte is 4, the zinc ion concentration is 120g/L, and the solid-to-liquid ratio g: mL of zinc powder to zinc sulfate solution is 3;
the concentration of cadmium ions in the zinc sulfate electrolyte purifying solution of the comparative example is 126.2mg/L.
Example 1: the zinc sulfate electrolyte was the same as comparative example 1;
a method for removing cadmium from zinc sulfate electrolyte by using zinc powder assisted by ultrasonic waves/copper ions comprises the following specific steps:
(1) Adding copper sulfate into zinc sulfate electrolyte containing cadmium ions, and adjusting the concentration of copper ions in the zinc sulfate electrolyte to 300mg/L to obtain pretreated zinc sulfate electrolyte; wherein the pH value of the zinc sulfate electrolyte is 4, and the concentration of zinc ions is 120g/L;
(2) Adding zinc powder (less than 200 meshes) serving as a reducing agent into the pretreated zinc sulfate electrolyte, performing ultrasonic enhanced replacement for 40min at the temperature of 55 ℃ and the stirring speed of 350rpm, performing solid-liquid separation to obtain purified slag and zinc sulfate electrolyte purified liquid, drying the purified slag, grinding, and detecting the concentration of cadmium ions in the zinc sulfate electrolyte purified liquid; wherein the solid-to-liquid ratio g: mL of the zinc powder to the zinc sulfate solution is 3;
the concentrations of cadmium ions and copper ions in the zinc sulfate electrolyte purified solution of this example are shown in table 2,
table 2 concentration of cadmium and copper ions in zinc sulfate electrolyte purification solution.
| Element(s) | Cd | Cu |
| Concentration (mg/L) | 31.9 | 0.9 |
The removal rates of cadmium ions and added copper ions in this example were 98.4% and 99.7%, respectively.
Example 2: the zinc sulfate electrolyte was the same as comparative example 1;
a method for removing cadmium from zinc sulfate electrolyte by using zinc powder assisted by ultrasonic waves/copper ions comprises the following specific steps:
(1) Adding copper sulfate into zinc sulfate electrolyte containing cadmium ions, and adjusting the concentration of copper ions in the zinc sulfate electrolyte to 400mg/L to obtain pretreated zinc sulfate electrolyte; wherein the pH value of the zinc sulfate electrolyte is 4.5, and the concentration of zinc ions is 120g/L;
(2) Adding zinc powder (less than 200 meshes) serving as a reducing agent into the pretreated zinc sulfate electrolyte, performing ultrasonic enhanced displacement for 45min at the temperature of 50 ℃ and the stirring speed of 400rpm, performing solid-liquid separation to obtain purified slag and a zinc sulfate electrolyte purified solution, drying the purified slag, grinding, and detecting the concentration of cadmium ions in the zinc sulfate electrolyte purified solution; wherein the solid-to-liquid ratio g: mL of the zinc powder to the zinc sulfate solution is 3;
the concentrations of cadmium ions and copper ions in the zinc sulfate electrolyte purified solution of this example are shown in table 3,
table 3 concentration of cadmium and copper ions in the zinc sulfate electrolyte purification solution.
| Element(s) | Cd | Cu |
| Concentration (mg/L) | 28.2 | 0.8 |
The removal rates of cadmium ions and added copper ions in this example were 98.6% and 99.8%, respectively.
Example 3: the zinc sulfate electrolyte was the same as in comparative example 1;
a method for removing cadmium from zinc sulfate electrolyte by using zinc powder assisted by ultrasonic waves/copper ions comprises the following steps:
(1) Adding copper sulfate into zinc sulfate electrolyte containing cadmium ions, and adjusting the concentration of copper ions in the zinc sulfate electrolyte to be 500mg/L to obtain pretreated zinc sulfate electrolyte; wherein the pH value of the zinc sulfate electrolyte is 4.5;
(2) Adding zinc powder (less than 200 meshes) as a reducing agent into the pretreated zinc sulfate electrolyte, performing ultrasonic enhanced replacement for 50min at the temperature of 60 ℃ and the stirring speed of 300rpm, performing solid-liquid separation to obtain purified slag and a zinc sulfate electrolyte purified solution, drying the purified slag, grinding, and detecting the concentration of cadmium ions in the zinc sulfate electrolyte purified solution; wherein the solid-to-liquid ratio g: mL of the zinc powder to the zinc sulfate solution is 3;
the concentrations of cadmium ions and copper ions in the zinc sulfate electrolyte purified solution of this example are shown in table 4,
table 4 concentration of cadmium and copper ions in zinc sulfate electrolyte purification solution.
| Element(s) | Cd | Cu |
| Concentration (mg/L) | 21.1 | 0.6 |
The removal rates of cadmium ions and added copper ions in this example were 98.9% and 99.88%, respectively.
Example 4: the zinc sulfate electrolyte was the same as in comparative example 1;
a method for removing cadmium from zinc sulfate electrolyte by using zinc powder assisted by ultrasonic waves/copper ions comprises the following specific steps:
(1) Adding copper sulfate into zinc sulfate electrolyte containing cadmium ions, and adjusting the concentration of copper ions in the zinc sulfate electrolyte to 600mg/L to obtain pretreated zinc sulfate electrolyte; wherein the pH value of the zinc sulfate electrolyte is 5;
(2) Adding zinc powder (less than 200 meshes) serving as a reducing agent into the pretreated zinc sulfate electrolyte, performing ultrasonic enhanced replacement for 50min at the temperature of 55 ℃ and the stirring speed of 350rpm, performing solid-liquid separation to obtain purified slag and zinc sulfate electrolyte purified liquid, drying the purified slag, grinding, and detecting the concentration of cadmium ions in the zinc sulfate electrolyte purified liquid; wherein the solid-to-liquid ratio g: mL of the zinc powder to the zinc sulfate solution is 3;
the concentrations of cadmium ions and copper ions in the zinc sulfate electrolyte purified solution of this example are shown in table 5,
table 5 concentration of cadmium and copper ions in zinc sulfate electrolyte purification solution.
| Element(s) | Cd | Cu |
| Concentration (mg/L) | 24.4 | 0.8 |
The removal rates of cadmium ions and added copper ions in this example were 98.78% and 99.87%, respectively.
Example 5: the zinc sulfate electrolyte was the same as comparative example 1;
a method for removing cadmium from zinc sulfate electrolyte by using zinc powder assisted by ultrasonic waves/copper ions comprises the following specific steps:
(1) Adding copper sulfate into zinc sulfate electrolyte containing cadmium ions, and adjusting the concentration of copper ions in the zinc sulfate electrolyte to 700mg/L to obtain pretreated zinc sulfate electrolyte; wherein the pH value of the zinc sulfate electrolyte is 4;
(2) Adding zinc powder (less than 200 meshes) serving as a reducing agent into the pretreated zinc sulfate electrolyte, performing ultrasonic enhanced replacement for 50min at the temperature of 50 ℃ and the stirring speed of 450rpm, performing solid-liquid separation to obtain purified slag and zinc sulfate electrolyte purified liquid, drying the purified slag, grinding, and detecting the concentration of cadmium ions in the zinc sulfate electrolyte purified liquid; wherein the solid-to-liquid ratio g: mL of the zinc powder to the zinc sulfate solution is 3;
the concentrations of cadmium ions and copper ions in the zinc sulfate electrolyte purified solution of the present example are shown in table 6,
table 6 concentration of cadmium and copper ions in zinc sulfate electrolyte purification solution.
| Element(s) | Cd | Cu |
| Concentration (mg/L) | 27.6 | 0.95 |
The removal rates of cadmium ions and added copper ions in this example were 98.62% and 99.86%, respectively.
While the present invention has been described in detail with reference to the specific embodiments thereof, the present invention is not limited to the embodiments described above, and various changes can be made without departing from the spirit of the present invention within the knowledge of those skilled in the art.
Claims (6)
1. A method for removing cadmium from zinc sulfate electrolyte by using zinc powder assisted by ultrasonic waves/copper ions is characterized by comprising the following specific steps:
(1) Adding copper sulfate into zinc sulfate electrolyte containing cadmium ions, and adjusting the concentration of copper ions in the zinc sulfate electrolyte to be 300-700mg/L to obtain pretreated zinc sulfate electrolyte;
(2) Adding zinc powder into the pretreated zinc sulfate electrolyte, performing ultrasonic enhanced replacement for 40-60min, performing solid-liquid separation to obtain purified slag and zinc sulfate electrolytic purified liquid, drying the purified slag, and grinding.
2. The ultrasonic/copper ion assisted zinc powder cadmium removal purification method from zinc sulfate electrolyte as claimed in claim 1, wherein: the concentration of zinc ions in the zinc sulfate electrolyte in the step (1) is 120-130g/L, and the concentration of cadmium ions is 15000-2000mg/L.
3. The method for purifying zinc powder from zinc sulfate electrolyte by assistance of ultrasonic waves/copper ions as claimed in claim 1, is characterized in that: the pH value of the zinc sulfate electrolyte in the step (1) is 4-5.
4. The ultrasonic/copper ion assisted zinc powder cadmium removal purification method from zinc sulfate electrolyte as claimed in claim 1, wherein: and (3) the solid-to-liquid ratio g: mL of the zinc powder to the pretreated zinc sulfate electrolyte in the step (2) is 2-3.
5. The ultrasonic/copper ion assisted zinc powder cadmium removal purification method from zinc sulfate electrolyte as claimed in claim 1, wherein: the ultrasonic power density in the step (2) is 160-240W/L, and the ultrasonic frequency is 19.63-19.73kHz.
6. The ultrasonic/copper ion assisted zinc powder cadmium removal purification method from zinc sulfate electrolyte as claimed in claim 1, wherein: the replacement temperature in the step (2) is 40-60 ℃.
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- 2022-11-10 CN CN202211407289.XA patent/CN115652373A/en active Pending
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| CN104561547A (en) * | 2014-12-23 | 2015-04-29 | 云南锡业股份有限公司 | Method for reducing zinc powder consumption in process of purifying zinc sulfate solution |
| CN110819821A (en) * | 2018-08-07 | 2020-02-21 | 昆明理工大学 | Method for intensively purifying zinc sulfate solution |
| CN112063855A (en) * | 2020-08-06 | 2020-12-11 | 云南云铜锌业股份有限公司 | Method for selectively purifying and removing copper and cadmium by automatic potential control |
| CN114182108A (en) * | 2021-12-15 | 2022-03-15 | 昆明理工大学 | Method for deep purification and copper and cadmium removal of zinc hydrometallurgy by combining ultrasonic wave with inert wet grinding reinforcement |
| CN114196838A (en) * | 2021-12-15 | 2022-03-18 | 昆明理工大学 | Ultrasonic wave and inert wet grinding combined method for deep purification and cobalt removal of zinc hydrometallurgy |
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