CA2872927C - Cadmium removing process in zinc-containing solution purification and purification method of zinc-containing solution - Google Patents
Cadmium removing process in zinc-containing solution purification and purification method of zinc-containing solution Download PDFInfo
- Publication number
- CA2872927C CA2872927C CA2872927A CA2872927A CA2872927C CA 2872927 C CA2872927 C CA 2872927C CA 2872927 A CA2872927 A CA 2872927A CA 2872927 A CA2872927 A CA 2872927A CA 2872927 C CA2872927 C CA 2872927C
- Authority
- CA
- Canada
- Prior art keywords
- zinc
- containing solution
- purification
- cadmium
- solid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B19/00—Obtaining zinc or zinc oxide
- C22B19/20—Obtaining zinc otherwise than by distilling
- C22B19/26—Refining solutions containing zinc values, e.g. obtained by leaching zinc ores
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/22—Treatment or purification of solutions, e.g. obtained by leaching by physical processes, e.g. by filtration, by magnetic means, or by thermal decomposition
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B19/00—Obtaining zinc or zinc oxide
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
- C22B3/46—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes by substitution, e.g. by cementation
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Geochemistry & Mineralogy (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
Disclosed are a cadmium removing process in zinc-containing solution purification with better cadmium removing effect and a purification method of zinc-containing solution with desired purification effect. The cadmium removing process in zinc-containing solution purification in the present invention includes following steps: 1) removing colloid from neutral leachate or supernatant of the neutral leachate after precipitation to obtain zinc-containing solution with colloid content less than or equal 50 mg/L; 2) performing zinc powder substitution in zinc-containing solution to at least replace cadmium; 3) carrying out solid-liquid separation to filter the zinc-containing solution containing impurity of cadmium, wherein filtering time is controlled within 60 minutes and filter precision is controlled within 10µm. In the present invention, the process of removing colloid from neutral leachate or supernatant first and then performing zinc powder substitution and filtration for solid-liquid separation is provided creatively and the selection and collocation of the key parameters such as colloid content in the zinc-containing solution after removing colloid and the filtering time and filter precision when filtering for solid-liquid separation is also provided to determine the final cadmium removing process.
Description
=
= CA 02872927 2014-11-07 Specification CADMIUM REMOVING PROCESS IN ZINC-CONTAINING SOLUTION
PURIFICATION AND PURIFICATION METHOD OF ZINC-CONTAINING SOLUTION
BACKGROUND
Technical Field The present invention relates to a purification process of zinc sulfate solution (referred to as zinc-containing solution hereinafter) in zinc hydrometallurgy, and in particular, to a process of removing impurities in a neutral leachate to be below a specified limit, so as to meet requirements for a fresh solution during electrolytic deposition.
Related Art In most existing purification methods of zinc-containing solution, neutral leachate is fed into a thickener for concentration, and zinc powder replacement is performed on supernatant (that is, medium-supernatant) after the concentration. For example, FIG.1 of CN101994005A shows a process of performing three periods of purification on supernatant, where the first period of purification removes copper, the second period of purification removes cobalt and nickel, and the third period of purification removes cadmium, and obtaining impurity-removed zinc-containing solution through solid-liquid separation for filtration after each period of purification.
Some zinc electrolysis plants directly perform zinc powder replacement on neutral leachate.
For example, a flow chart of a text of "Design for Zinc-Containing Solution Purification Process in Zinc Electrolysis Plant, Yang Lian, Engineering Design and Research, Vol.
119, June, 2006"
shows a process of performing three periods of purification on neutral leachate, where the first period of purification removes copper and cadmium, the second period of purification removes cobalt and nickel, and the third period of purification further removes cadmium, and obtaining impurity-removed zinc-containing solution through solid-liquid separation for filtration after each period of purification.
In brief, the current research trends on zinc-containing solution purification process indicate that improvement on the zinc-containing solution purification process always focuses on zinc powder replacement, and there are few researches involving processing on neutral leachate or supernatant of the neutral leachate after precipitation.
Even so, the problem of deep purification of cadmium has never been completely resolved.
An important reason lies in that, in the existing zinc-containing solution purification processes, basically a filter cloth is used as a filtering element for solid-liquid separation, however, the general filter cloths have limited filtering precision, which easily causes the penetration of cadmium; in this case, replaced cadmium is quite easily dissolved. Therefore, the two reference documents both adopt the three-period purification process, and cadmium removing is involved in the last period of purification, it can be seen that the fundamental objective is to improve the purification level of cadmium. Obviously, the three-period purification process is very long and consumes a large amount of zinc powder.
SUMMARY
A technical problem to be solved in the present invention is to provide a cadmium removing process in zinc-containing solution purification, so as to achieve a better cadmium removing effect.
Next, the present invention further provides a purification method of zinc-containing solution with an ideal purification effect and a filtration residue obtained by using the method, and high purity solid zinc in the filtration residue may be used subsequently.
First, the cadmium removing process in zinc-containing solution purification of the present invention includes the following steps: 1) removing colloid from neutral leachate or supernatant of = CA 02872927 2014-11-07 the neutral leachate after precipitation to obtain zinc-containing solution with colloid content below 50 mg/L; 2) performing zinc powder replacement in zinc-containing solution to at least replace cadmium; and 3) carrying out solid-liquid separation to filter the zinc-containing solution containing impurity of cadmium, where filtering time is controlled within 60 minutes and filter precision is controlled below 10 gm.
The colloid in the neutral leachate or the supernatant of the neutral leachate after precipitation mainly includes substances such as silica gel and iron gel, and the colloid substances exist in an agglomeration form in the zinc-containing solution. The colloid content in general medium-supernatant is about 1 g/L, and the colloid content in the neutral leachate is greater. Due to the existence of colloid substances, the zinc powder replacement effect is reduced, and solid-liquid separation for filtration is blocked, which greatly affects the cadmium removing effect.
In view of this, the present invention creatively adopts a process of the first removing colloid from neutral leachate or supernatant and then performing zinc powder replacement and solid-liquid separation for filtration, and selection and collocation of key parameters such as colloid content in the zinc-containing solution after removing colloid and the filtering time and filter precision during solid-liquid separation for filtration are also provided to determine the final cadmium removing process. Before the present invention, zinc-containing solution is prepared by performing zinc powder replacement on the neutral leachate or the supernatant of the neutral leachate after precipitation to carry out the first period of purification to remove cadmium, and performing solid-liquid separation for filtration has a cadmium content of about 20-50 mg/L.
Experiments show, cadmium ion content in the zinc-containing solution prepared by performing zinc powder replacement on the neutral leachate or the supernatant of the neutral leachate after precipitation to carry out the first period of purification, and performing solid-liquid separation filtering is below 2 mg/L.
In the step 1) of the cadmium removing process of the present invention, the colloid removing process may be performed in different manners. For example, a flocculant or an electrolyte may be added into the zinc-containing solution to precipitate the colloid substances.
However, preferably, the step 1) is implemented by performing membrane filtration on the neutral leachate or the supernatant. The membrane filtration can not only remove the colloid substances in the zinc-containing solution, but also remove solid impurities such as ZnFe02, so that the zinc-containing solution prior to the replacement reaction has a better quality, thereby further improving the purification effect of the zinc-containing solution. In order to prevent a filter cake from being formed too quickly to reduce the filtration flux, the step 1) is preferably implemented by performing cross-flow membrane filtration on the neutral leachate or the supernatant. The cross-flow filtration has a special effect on colloid removing: the shear force of the cross-flow filtration can effectively prevent the colloid from attaching to the surface of the filter element, thereby reducing the thickness of a filter cake layer, and ensuring the filtration flux.
It is also suggested that the step 3) is implemented by using the membrane filtration. To implement fast filtration, terminal membrane filtration is preferred.
The purification method of zinc-containing solution of the present invention includes the following steps: 1) removing colloid from neutral leachate or supernatant of the neutral leachate after precipitation to obtain zinc-containing solution with colloid content less than or equal to 50 mg/L; 2) performing first zinc powder replacement in zinc-containing solution to at least remove copper and cadmium; 3) carrying out solid-liquid separation to filter the zinc-containing solution containing solid impurities of copper and cadmium, where filtering time is controlled within 60 minutes and filter precision is controlled below 10 gm; 4) carrying out a second period of purification on the zinc-containing solution after the solid-liquid separation for filtration to at least remove cobalt and nickel; and 5) carrying out solid-liquid separation to filter the zinc-containing solution containing solid impurities of cobalt and nickel, so as to obtain a fresh solution and a filtration residue.
Experiments show that, in the filtration residue obtained by means of the above method, the weight ratio of three solid substances, namely, copper, cadmium and cobalt to solid zinc is Cu: Cd:
Co: Zn= (0.01-0.2): (0-0.001): (0.5-1.5): 100. It can be seen that, in the filtration residue, the weight ratio of the solid cadmium to the solid zinc is less than 1 X 10-5, and the cadmium content
= CA 02872927 2014-11-07 Specification CADMIUM REMOVING PROCESS IN ZINC-CONTAINING SOLUTION
PURIFICATION AND PURIFICATION METHOD OF ZINC-CONTAINING SOLUTION
BACKGROUND
Technical Field The present invention relates to a purification process of zinc sulfate solution (referred to as zinc-containing solution hereinafter) in zinc hydrometallurgy, and in particular, to a process of removing impurities in a neutral leachate to be below a specified limit, so as to meet requirements for a fresh solution during electrolytic deposition.
Related Art In most existing purification methods of zinc-containing solution, neutral leachate is fed into a thickener for concentration, and zinc powder replacement is performed on supernatant (that is, medium-supernatant) after the concentration. For example, FIG.1 of CN101994005A shows a process of performing three periods of purification on supernatant, where the first period of purification removes copper, the second period of purification removes cobalt and nickel, and the third period of purification removes cadmium, and obtaining impurity-removed zinc-containing solution through solid-liquid separation for filtration after each period of purification.
Some zinc electrolysis plants directly perform zinc powder replacement on neutral leachate.
For example, a flow chart of a text of "Design for Zinc-Containing Solution Purification Process in Zinc Electrolysis Plant, Yang Lian, Engineering Design and Research, Vol.
119, June, 2006"
shows a process of performing three periods of purification on neutral leachate, where the first period of purification removes copper and cadmium, the second period of purification removes cobalt and nickel, and the third period of purification further removes cadmium, and obtaining impurity-removed zinc-containing solution through solid-liquid separation for filtration after each period of purification.
In brief, the current research trends on zinc-containing solution purification process indicate that improvement on the zinc-containing solution purification process always focuses on zinc powder replacement, and there are few researches involving processing on neutral leachate or supernatant of the neutral leachate after precipitation.
Even so, the problem of deep purification of cadmium has never been completely resolved.
An important reason lies in that, in the existing zinc-containing solution purification processes, basically a filter cloth is used as a filtering element for solid-liquid separation, however, the general filter cloths have limited filtering precision, which easily causes the penetration of cadmium; in this case, replaced cadmium is quite easily dissolved. Therefore, the two reference documents both adopt the three-period purification process, and cadmium removing is involved in the last period of purification, it can be seen that the fundamental objective is to improve the purification level of cadmium. Obviously, the three-period purification process is very long and consumes a large amount of zinc powder.
SUMMARY
A technical problem to be solved in the present invention is to provide a cadmium removing process in zinc-containing solution purification, so as to achieve a better cadmium removing effect.
Next, the present invention further provides a purification method of zinc-containing solution with an ideal purification effect and a filtration residue obtained by using the method, and high purity solid zinc in the filtration residue may be used subsequently.
First, the cadmium removing process in zinc-containing solution purification of the present invention includes the following steps: 1) removing colloid from neutral leachate or supernatant of = CA 02872927 2014-11-07 the neutral leachate after precipitation to obtain zinc-containing solution with colloid content below 50 mg/L; 2) performing zinc powder replacement in zinc-containing solution to at least replace cadmium; and 3) carrying out solid-liquid separation to filter the zinc-containing solution containing impurity of cadmium, where filtering time is controlled within 60 minutes and filter precision is controlled below 10 gm.
The colloid in the neutral leachate or the supernatant of the neutral leachate after precipitation mainly includes substances such as silica gel and iron gel, and the colloid substances exist in an agglomeration form in the zinc-containing solution. The colloid content in general medium-supernatant is about 1 g/L, and the colloid content in the neutral leachate is greater. Due to the existence of colloid substances, the zinc powder replacement effect is reduced, and solid-liquid separation for filtration is blocked, which greatly affects the cadmium removing effect.
In view of this, the present invention creatively adopts a process of the first removing colloid from neutral leachate or supernatant and then performing zinc powder replacement and solid-liquid separation for filtration, and selection and collocation of key parameters such as colloid content in the zinc-containing solution after removing colloid and the filtering time and filter precision during solid-liquid separation for filtration are also provided to determine the final cadmium removing process. Before the present invention, zinc-containing solution is prepared by performing zinc powder replacement on the neutral leachate or the supernatant of the neutral leachate after precipitation to carry out the first period of purification to remove cadmium, and performing solid-liquid separation for filtration has a cadmium content of about 20-50 mg/L.
Experiments show, cadmium ion content in the zinc-containing solution prepared by performing zinc powder replacement on the neutral leachate or the supernatant of the neutral leachate after precipitation to carry out the first period of purification, and performing solid-liquid separation filtering is below 2 mg/L.
In the step 1) of the cadmium removing process of the present invention, the colloid removing process may be performed in different manners. For example, a flocculant or an electrolyte may be added into the zinc-containing solution to precipitate the colloid substances.
However, preferably, the step 1) is implemented by performing membrane filtration on the neutral leachate or the supernatant. The membrane filtration can not only remove the colloid substances in the zinc-containing solution, but also remove solid impurities such as ZnFe02, so that the zinc-containing solution prior to the replacement reaction has a better quality, thereby further improving the purification effect of the zinc-containing solution. In order to prevent a filter cake from being formed too quickly to reduce the filtration flux, the step 1) is preferably implemented by performing cross-flow membrane filtration on the neutral leachate or the supernatant. The cross-flow filtration has a special effect on colloid removing: the shear force of the cross-flow filtration can effectively prevent the colloid from attaching to the surface of the filter element, thereby reducing the thickness of a filter cake layer, and ensuring the filtration flux.
It is also suggested that the step 3) is implemented by using the membrane filtration. To implement fast filtration, terminal membrane filtration is preferred.
The purification method of zinc-containing solution of the present invention includes the following steps: 1) removing colloid from neutral leachate or supernatant of the neutral leachate after precipitation to obtain zinc-containing solution with colloid content less than or equal to 50 mg/L; 2) performing first zinc powder replacement in zinc-containing solution to at least remove copper and cadmium; 3) carrying out solid-liquid separation to filter the zinc-containing solution containing solid impurities of copper and cadmium, where filtering time is controlled within 60 minutes and filter precision is controlled below 10 gm; 4) carrying out a second period of purification on the zinc-containing solution after the solid-liquid separation for filtration to at least remove cobalt and nickel; and 5) carrying out solid-liquid separation to filter the zinc-containing solution containing solid impurities of cobalt and nickel, so as to obtain a fresh solution and a filtration residue.
Experiments show that, in the filtration residue obtained by means of the above method, the weight ratio of three solid substances, namely, copper, cadmium and cobalt to solid zinc is Cu: Cd:
Co: Zn= (0.01-0.2): (0-0.001): (0.5-1.5): 100. It can be seen that, in the filtration residue, the weight ratio of the solid cadmium to the solid zinc is less than 1 X 10-5, and the cadmium content
2 =
is extremely low.
In the purification method of zinc-containing solution, second zinc powder replacement may be performed on the zinc-containing solution to carry out a second period of purification to remove cobalt and nickel, or xanthate, [3-naphthol and nickel may be added to the zinc-containing solution to remove cobalt and nickel.
Based on the described reason, the step 1) is implemented by performing membrane filtration on the neutral leachate or the supernatant.
Based on the described reason, the step 1) is implemented by performing cross-flow membrane filtration on the neutral leachate or the supernatant.
As further improvement of the purification method of zinc-containing solution, the filtration residue obtained in the step 5) serves as a zinc powder raw material used for performing the zinc powder replacement in the above step. By means of the first period of purification and solid-liquid separation performed on the zinc-containing solution containing solid impurities of copper and cadmium, the content of cadmium ions in the zinc-containing solution after filtration is greatly reduced, and therefore, the filtration residue obtained by means of the second period of purification and solid-liquid separation performed on the zinc-containing solution containing solid impurities of cobalt and nickel only contains very little cadmium; in this case, the filtration residue absolutely can be returned to the previous step to serve as the zinc powder raw material used for performing the zinc powder replacement; therefore, the consumption of zinc powder is significantly reduced without any adverse effect on the purification process of zinc-containing solution (almost no impurity cadmium is introduced into the zinc-containing solution). In the past, the cadmium content in the filtration residue after purification of the zinc-containing solution is high, and persons skilled in the art cannot use the filtration residue as the zinc powder raw material.
For the step 3) and the step 4), at least the step 3) adopts membrane filtration.
For the step 3) and the step 4), at least the step 3) adopts terminal membrane filtration.
In the filtration residue provided in the present invention and obtained after purification of the zinc-containing solution, the weight ratio of solid cadmium to solid zinc is less than 1 X 10-5.
The filtration residue is the zinc powder raw material used in zinc powder replacement during zinc-containing solution purification.
The filtration residue is obtained by using the following purification method of zinc-containing solution, and the method includes the following steps: 1) removing colloid from neutral leachate or supernatant of the neutral leachate after precipitation to obtain zinc-containing solution with colloid content below 50 mg/L; 2) performing first zinc powder replacement in zinc-containing solution to perform a first period of purification to at least remove copper and cadmium; 3) carrying out solid-liquid separation to filter the zinc-containing solution containing solid impurities of copper and cadmium, where filtering time is controlled within 60 minutes and filter precision is controlled below 10 iim; 4) carrying out a second period of purification on the zinc-containing solution after the solid-liquid separation for filtration to at least remove cobalt and nickel; and 5) performing solid-liquid separation to filter the zinc-containing solution containing solid impurities of cobalt and nickel, so as to obtain a fresh solution and a filtration residue.
The step 1) is implemented by performing membrane filtration on the neutral leachate or the supernatant.
The step 1) is implemented by performing cross-flow membrane filtration on the neutral leachate or the supernatant.
Further, after the step 1) of removing the colloid from the neutral leachate or the supernatant, a zinc-containing solution with colloid content below 10 mg,/L is obtained.
The second zinc powder replacement is performed on the zinc-containing solution to carry out the second period of purification to at least remove cobalt and nickel.
For the step 3) and the step 4), at least the step 3) adopts membrane filtration.
is extremely low.
In the purification method of zinc-containing solution, second zinc powder replacement may be performed on the zinc-containing solution to carry out a second period of purification to remove cobalt and nickel, or xanthate, [3-naphthol and nickel may be added to the zinc-containing solution to remove cobalt and nickel.
Based on the described reason, the step 1) is implemented by performing membrane filtration on the neutral leachate or the supernatant.
Based on the described reason, the step 1) is implemented by performing cross-flow membrane filtration on the neutral leachate or the supernatant.
As further improvement of the purification method of zinc-containing solution, the filtration residue obtained in the step 5) serves as a zinc powder raw material used for performing the zinc powder replacement in the above step. By means of the first period of purification and solid-liquid separation performed on the zinc-containing solution containing solid impurities of copper and cadmium, the content of cadmium ions in the zinc-containing solution after filtration is greatly reduced, and therefore, the filtration residue obtained by means of the second period of purification and solid-liquid separation performed on the zinc-containing solution containing solid impurities of cobalt and nickel only contains very little cadmium; in this case, the filtration residue absolutely can be returned to the previous step to serve as the zinc powder raw material used for performing the zinc powder replacement; therefore, the consumption of zinc powder is significantly reduced without any adverse effect on the purification process of zinc-containing solution (almost no impurity cadmium is introduced into the zinc-containing solution). In the past, the cadmium content in the filtration residue after purification of the zinc-containing solution is high, and persons skilled in the art cannot use the filtration residue as the zinc powder raw material.
For the step 3) and the step 4), at least the step 3) adopts membrane filtration.
For the step 3) and the step 4), at least the step 3) adopts terminal membrane filtration.
In the filtration residue provided in the present invention and obtained after purification of the zinc-containing solution, the weight ratio of solid cadmium to solid zinc is less than 1 X 10-5.
The filtration residue is the zinc powder raw material used in zinc powder replacement during zinc-containing solution purification.
The filtration residue is obtained by using the following purification method of zinc-containing solution, and the method includes the following steps: 1) removing colloid from neutral leachate or supernatant of the neutral leachate after precipitation to obtain zinc-containing solution with colloid content below 50 mg/L; 2) performing first zinc powder replacement in zinc-containing solution to perform a first period of purification to at least remove copper and cadmium; 3) carrying out solid-liquid separation to filter the zinc-containing solution containing solid impurities of copper and cadmium, where filtering time is controlled within 60 minutes and filter precision is controlled below 10 iim; 4) carrying out a second period of purification on the zinc-containing solution after the solid-liquid separation for filtration to at least remove cobalt and nickel; and 5) performing solid-liquid separation to filter the zinc-containing solution containing solid impurities of cobalt and nickel, so as to obtain a fresh solution and a filtration residue.
The step 1) is implemented by performing membrane filtration on the neutral leachate or the supernatant.
The step 1) is implemented by performing cross-flow membrane filtration on the neutral leachate or the supernatant.
Further, after the step 1) of removing the colloid from the neutral leachate or the supernatant, a zinc-containing solution with colloid content below 10 mg,/L is obtained.
The second zinc powder replacement is performed on the zinc-containing solution to carry out the second period of purification to at least remove cobalt and nickel.
For the step 3) and the step 4), at least the step 3) adopts membrane filtration.
3 For the step 3) and the step 4), at least the step 3) adopts terminal membrane filtration.
The preparation method of the filtration residue obtained after zinc-containing solution purification includes the following steps: 1) removing colloid from neutral leachate or supernatant of the neutral leachate after precipitation to obtain zinc-containing solution with colloid content below 50 mg/L;
2) performing first zinc powder replacement in zinc-containing solution to carry out a first period of putification to at least remove copper and cadmium; 3) carrying out solid-liquid separation to filter the zinc-containing solution containing solid impurities of copper and cadmium, where filtering time is controlled within 60 minutes and filter precision is controlled below 10 gm;
The preparation method of the filtration residue obtained after zinc-containing solution purification includes the following steps: 1) removing colloid from neutral leachate or supernatant of the neutral leachate after precipitation to obtain zinc-containing solution with colloid content below 50 mg/L;
2) performing first zinc powder replacement in zinc-containing solution to carry out a first period of putification to at least remove copper and cadmium; 3) carrying out solid-liquid separation to filter the zinc-containing solution containing solid impurities of copper and cadmium, where filtering time is controlled within 60 minutes and filter precision is controlled below 10 gm;
4) carrying out a second period of purification on the zinc-containing solution after the solid-liquid separation to at least remove cobalt and nickel; and 5) carrying out solid-liquid separation to filter the zinc-containing solution containing solid impurities of cobalt and nickel, so as to obtain a fresh solution and a filtration residue.
The present invention as claimed relates to:
- a cadmium removing process in zinc-containing solution purification, comprising;
1) removing colloid from neutral leachate or supernatant of the neutral leachate after precipitation to obtain zinc-containing solution with colloid content below 10 mg/L; 2) performing zinc powder replacement in the zinc-containing solution to at least replace cadmium; and 3) carrying out solid-liquid separation to filter the zinc-containing solution containing solid impurity of cadmium, wherein filtering time is controlled to be within 60 minutes and filter precision is controlled to be below 10 gm, wherein the step 1) is implemented by performing cross-flow membrane filtration on the neutral leachate or the supernatant, and the step 3) adopts a terminal membrane filtration; and - a method of purifying zinc-containing solution, comprising: 1) removing colloid from neutral leachate or supernatant of the neutral leachate after precipitation to obtain zinc-containing solution with colloid content below 10 mg/L; 2) performing first zinc powder replacement in zinc-containing solution to carry out a first period of purification to at least remove copper and cadmium; 3) carrying out solid-liquid separation to filter the zinc-containing solution containing solid impurities of copper and cadmium, where filtering time is controlled to be within 60 minutes and filter precision is controlled to be below 10 gm; 4) carrying out a second period of purification on the zinc-containing solution after the solid-liquid separation for filtration to at least remove cobalt and nickel; and 5) carrying out solid-liquid separation to filter the zinc-containing solution containing solid impurities of cobalt and nickel, so as to obtain a fresh solution and a filtration residue, wherein in the filtration residue, the weight ratio of the solid cadmium to the solid zinc is less than 1x105, and wherein the step 1) is implemented by performing cross-flow membrane filtration on the neutral leachate or the supernatant, and for the step 3) and the step 4), at least the step 3) adopts a terminal membrane filtration.
BRIEF DESCRIPTION OF THE DRAWING
FIG.1 is a process flow chart of a specific implementation of a purification method of zinc-containing solution according to the present invention.
DETAILED DESCRIPTION
In supernatant obtained from neutral leachate after precipitation of a certain zinc electrolysis plant, copper ion content, cadmium ion content, and cobalt ion content are respectively 400 mg/L, 550 mg/L, and 25 mg/L, and it is measured that colloid content in the solution is 1 g/L. The zinc electrolysis plant currently uses a three-period purification process, in which, the first zinc powder replacement is performed on the supernatant to carry out a first period of purification to at least remove copper and cadmium; solid-liquid separation is carried out to filter the zinc-containing solution containing solid impurities of copper and cadmium, where a plate-and-frame filter press is used during filtering, filtering precision of the filler cloth in the plate-and-frame filter press is 40-50 [tm, and filtering time is 60 minutes; the second zinc powder replacement is performed to carry out a second period of purification on the zinc-containing solution to at least remove cobalt and nickel; solid-liquid separation is carried out to filter the zinc-containing solution containing solid impurities of cobalt and nickel, where the same plate-and-frame filter press is used during filtering, and filtering time is 40 minutes; the third zinc powder replacement is performed to carry out a third period of purification on the zinc-containing solution to at least remove cadmium; and solid-liquid separation is carried out to filter the zinc-containing solution containing solid impurity of cadmium by using the same plate-and-frame filter press, so as to obtain a fresh solution and a filtration residue. Measurements The measurement data show that, in the zinc-containing solution after the first period of purification and filtering, copper ion content, cadmium ion content, and cobalt ion content are respectively 12 mg/L, 50 mg/L, and 20 mg/L; in the zinc-containing solution after the second period of purification and filtering, copper ion content, cadmium ion content, and cobalt ion content are respectively 0.4 mg/L, 2.0 mg/L, and 1.5 mg/L; and in the zinc-containing solution after the third period of purification and filtering, copper ion content, cadmium ion content, and cobalt ion content are respectively 0.1 mg/L, 0.8 mg/L, and 1.0 mg/L.
As shown in F1G.1, the following method is performed on the same supernatant in the present invention, including the steps of: 1) removing colloid from the supernatant by using cross-flow membrane filtration to obtain zinc-containing solution with colloid content below 50 mg/L; 2) performing the first zinc powder replacement (using process conditions of removing copper and cadmium in the 4a existing zinc powder replacement) in zinc-containing solution to carry out a first period of purification to at least remove copper and cadmium; 3) carrying out solid-liquid separation to filter the zinc-containing solution containing solid impurities of copper and cadmium by using terminal membrane filtration, where filtering time is controlled within 60 minutes and filter precision is controlled below 10 p.m; 4) performing the second zinc powder replacement (using process conditions of removing cobalt and nickel in the existing zinc powder replacement) on the zinc-containing solution after the solid-liquid separation for filtration to carry out the second period of purification to at least remove cobalt and nickel; and 5) carrying out solid-liquid separation to filter the zinc-containing solution containing solid impurities of cobalt and nickel by using terminal membrane filtration, so as to obtain a fresh solution and a filtration residue. The filtration residue returns to the processes of the first period of purification and the 4b = CA 02872927 2014-11-07 1'CT/CN2012/079545 second period of purification as a zinc powder raw material used for performing the zinc powder replacement; and dregs generated during filtration in the purification process of zinc-containing solution is discharged through a first terminal membrane filtration outlet.
The purification method of zinc-containing solution of the present invention is described specifically by means of the following 5 embodiments (numbered 1 to 5), and details may be obtained with reference to Table 1.
In addition, the measurements show that in the filtration residues after the second period of purification in the 5 embodiments, the weight ratio of three solid substances, namely copper, cadmium, and cobalt to solid zinc is Cu: Cd: Co: Zn= (0.01-0.2): (0-0.001):
(0.5-1.5): 100. That is to say, in the filtration residue, the weight ratio of the solid cadmium to the solid zinc is less than 1 X le, and the cadmium content is extremely low.
It should be particularly noted that:
1. The term "filtering time" refers to time used for filtering a certain amount of zinc-containing solution from beginning of the filtration to completion of the filtration.
2. The colloid content of the zinc-containing solution may be measured by using a method in nephelometry such as a gravimetric method, and spectrophotometry.
Table 1 Colloid Some metal ion Some metal ion content in Filtering contents in contents in Filtering parameters solution Number after the first period parameters after solution after the solution after the after the second period first period of second period of of purification colloid of purification purification and purification and removing filtration filtration Cu (mg/L): 2 Cu (mg/L): 0.1 Filtering time: 60 Filtering time: 60 Cd (mg/L): 2.0 Cd (mg/L): 1.2 min min 1 50 mg/L
Filtering precision: Filtering precision:
um 10 um Co (mg/L): 25 Co (mg/L): 1.0 Filtering time: 60 Filtering time: 60 Cu (mg/L): 2 Cu (mg/L): 0.1 min min Cd (mg/L): 1.69 Cd (mg/L): 1.0 2 30 mg/L
Filtering precision: Filtering precision:
10 um 10 um Co (mg/L): 23 Co (mg/L): 1.0 Cu (mg/L): 2 Cu (mg/L): 0.1 Filtering time: 60 Filtering time: 60 Cd (mg/L): 1.0 Cd (mg/L): 0.7 min min 3 10 mg/L
Filtering precision: Filtering precision:
Co (mg/L): 18 Co (mg/L): 1.0 10 um 10 um Cu (mg/L): 1.5 Cu (mg/L): 0.1 Filtering time: 30 Filtering time: 30 Cd (mg/L): Cd (mg/L):
min min wave-free wave-free 8 mg/L Filtering precision: Filtering precision:
10 um 10 um Co (mg/L): 20 Co (mg/L): 1.0 Cu (mg/L): 1.2 Cu (mg/L): 0.1 Filtering time: 30 Filtering time: 30 Cd (mg/L): Cd (mg/L):
min min wave-free wave-free
The present invention as claimed relates to:
- a cadmium removing process in zinc-containing solution purification, comprising;
1) removing colloid from neutral leachate or supernatant of the neutral leachate after precipitation to obtain zinc-containing solution with colloid content below 10 mg/L; 2) performing zinc powder replacement in the zinc-containing solution to at least replace cadmium; and 3) carrying out solid-liquid separation to filter the zinc-containing solution containing solid impurity of cadmium, wherein filtering time is controlled to be within 60 minutes and filter precision is controlled to be below 10 gm, wherein the step 1) is implemented by performing cross-flow membrane filtration on the neutral leachate or the supernatant, and the step 3) adopts a terminal membrane filtration; and - a method of purifying zinc-containing solution, comprising: 1) removing colloid from neutral leachate or supernatant of the neutral leachate after precipitation to obtain zinc-containing solution with colloid content below 10 mg/L; 2) performing first zinc powder replacement in zinc-containing solution to carry out a first period of purification to at least remove copper and cadmium; 3) carrying out solid-liquid separation to filter the zinc-containing solution containing solid impurities of copper and cadmium, where filtering time is controlled to be within 60 minutes and filter precision is controlled to be below 10 gm; 4) carrying out a second period of purification on the zinc-containing solution after the solid-liquid separation for filtration to at least remove cobalt and nickel; and 5) carrying out solid-liquid separation to filter the zinc-containing solution containing solid impurities of cobalt and nickel, so as to obtain a fresh solution and a filtration residue, wherein in the filtration residue, the weight ratio of the solid cadmium to the solid zinc is less than 1x105, and wherein the step 1) is implemented by performing cross-flow membrane filtration on the neutral leachate or the supernatant, and for the step 3) and the step 4), at least the step 3) adopts a terminal membrane filtration.
BRIEF DESCRIPTION OF THE DRAWING
FIG.1 is a process flow chart of a specific implementation of a purification method of zinc-containing solution according to the present invention.
DETAILED DESCRIPTION
In supernatant obtained from neutral leachate after precipitation of a certain zinc electrolysis plant, copper ion content, cadmium ion content, and cobalt ion content are respectively 400 mg/L, 550 mg/L, and 25 mg/L, and it is measured that colloid content in the solution is 1 g/L. The zinc electrolysis plant currently uses a three-period purification process, in which, the first zinc powder replacement is performed on the supernatant to carry out a first period of purification to at least remove copper and cadmium; solid-liquid separation is carried out to filter the zinc-containing solution containing solid impurities of copper and cadmium, where a plate-and-frame filter press is used during filtering, filtering precision of the filler cloth in the plate-and-frame filter press is 40-50 [tm, and filtering time is 60 minutes; the second zinc powder replacement is performed to carry out a second period of purification on the zinc-containing solution to at least remove cobalt and nickel; solid-liquid separation is carried out to filter the zinc-containing solution containing solid impurities of cobalt and nickel, where the same plate-and-frame filter press is used during filtering, and filtering time is 40 minutes; the third zinc powder replacement is performed to carry out a third period of purification on the zinc-containing solution to at least remove cadmium; and solid-liquid separation is carried out to filter the zinc-containing solution containing solid impurity of cadmium by using the same plate-and-frame filter press, so as to obtain a fresh solution and a filtration residue. Measurements The measurement data show that, in the zinc-containing solution after the first period of purification and filtering, copper ion content, cadmium ion content, and cobalt ion content are respectively 12 mg/L, 50 mg/L, and 20 mg/L; in the zinc-containing solution after the second period of purification and filtering, copper ion content, cadmium ion content, and cobalt ion content are respectively 0.4 mg/L, 2.0 mg/L, and 1.5 mg/L; and in the zinc-containing solution after the third period of purification and filtering, copper ion content, cadmium ion content, and cobalt ion content are respectively 0.1 mg/L, 0.8 mg/L, and 1.0 mg/L.
As shown in F1G.1, the following method is performed on the same supernatant in the present invention, including the steps of: 1) removing colloid from the supernatant by using cross-flow membrane filtration to obtain zinc-containing solution with colloid content below 50 mg/L; 2) performing the first zinc powder replacement (using process conditions of removing copper and cadmium in the 4a existing zinc powder replacement) in zinc-containing solution to carry out a first period of purification to at least remove copper and cadmium; 3) carrying out solid-liquid separation to filter the zinc-containing solution containing solid impurities of copper and cadmium by using terminal membrane filtration, where filtering time is controlled within 60 minutes and filter precision is controlled below 10 p.m; 4) performing the second zinc powder replacement (using process conditions of removing cobalt and nickel in the existing zinc powder replacement) on the zinc-containing solution after the solid-liquid separation for filtration to carry out the second period of purification to at least remove cobalt and nickel; and 5) carrying out solid-liquid separation to filter the zinc-containing solution containing solid impurities of cobalt and nickel by using terminal membrane filtration, so as to obtain a fresh solution and a filtration residue. The filtration residue returns to the processes of the first period of purification and the 4b = CA 02872927 2014-11-07 1'CT/CN2012/079545 second period of purification as a zinc powder raw material used for performing the zinc powder replacement; and dregs generated during filtration in the purification process of zinc-containing solution is discharged through a first terminal membrane filtration outlet.
The purification method of zinc-containing solution of the present invention is described specifically by means of the following 5 embodiments (numbered 1 to 5), and details may be obtained with reference to Table 1.
In addition, the measurements show that in the filtration residues after the second period of purification in the 5 embodiments, the weight ratio of three solid substances, namely copper, cadmium, and cobalt to solid zinc is Cu: Cd: Co: Zn= (0.01-0.2): (0-0.001):
(0.5-1.5): 100. That is to say, in the filtration residue, the weight ratio of the solid cadmium to the solid zinc is less than 1 X le, and the cadmium content is extremely low.
It should be particularly noted that:
1. The term "filtering time" refers to time used for filtering a certain amount of zinc-containing solution from beginning of the filtration to completion of the filtration.
2. The colloid content of the zinc-containing solution may be measured by using a method in nephelometry such as a gravimetric method, and spectrophotometry.
Table 1 Colloid Some metal ion Some metal ion content in Filtering contents in contents in Filtering parameters solution Number after the first period parameters after solution after the solution after the after the second period first period of second period of of purification colloid of purification purification and purification and removing filtration filtration Cu (mg/L): 2 Cu (mg/L): 0.1 Filtering time: 60 Filtering time: 60 Cd (mg/L): 2.0 Cd (mg/L): 1.2 min min 1 50 mg/L
Filtering precision: Filtering precision:
um 10 um Co (mg/L): 25 Co (mg/L): 1.0 Filtering time: 60 Filtering time: 60 Cu (mg/L): 2 Cu (mg/L): 0.1 min min Cd (mg/L): 1.69 Cd (mg/L): 1.0 2 30 mg/L
Filtering precision: Filtering precision:
10 um 10 um Co (mg/L): 23 Co (mg/L): 1.0 Cu (mg/L): 2 Cu (mg/L): 0.1 Filtering time: 60 Filtering time: 60 Cd (mg/L): 1.0 Cd (mg/L): 0.7 min min 3 10 mg/L
Filtering precision: Filtering precision:
Co (mg/L): 18 Co (mg/L): 1.0 10 um 10 um Cu (mg/L): 1.5 Cu (mg/L): 0.1 Filtering time: 30 Filtering time: 30 Cd (mg/L): Cd (mg/L):
min min wave-free wave-free 8 mg/L Filtering precision: Filtering precision:
10 um 10 um Co (mg/L): 20 Co (mg/L): 1.0 Cu (mg/L): 1.2 Cu (mg/L): 0.1 Filtering time: 30 Filtering time: 30 Cd (mg/L): Cd (mg/L):
min min wave-free wave-free
5 8 mg/L
Filtering precision: Filtering precision:
7 um 7 um Co (mg/L): 18 Co (mg/L): 1.0 Note: "Wave-free" refers to an element that cannot be detected by the polarograph method.
Filtering precision: Filtering precision:
7 um 7 um Co (mg/L): 18 Co (mg/L): 1.0 Note: "Wave-free" refers to an element that cannot be detected by the polarograph method.
Claims (4)
1. A cadmium removing process in zinc-containing solution purification, comprising: 1) removing colloid from neutral leachate or supernatant of the neutral leachate after precipitation to obtain zinc-containing solution with colloid content below 10 mg/L; 2) performing zinc powder replacement in the zinc-containing solution to at least replace cadmium; and 3) carrying out solid-liquid separation to filter the zinc-containing solution containing solid impurity of cadmium, wherein filtering time is controlled to be within 60 minutes and filter precision is controlled to be below 10 µ, wherein the step 1) is implemented by performing cross-flow membrane filtration on the neutral leachate or the supernatant, and the step 3) adopts a terminal membrane filtration.
2. A method of purifying zinc-containing solution, comprising: 1) removing colloid from neutral leachate or supernatant of the neutral leachate after precipitation to obtain zinc-containing solution with colloid content below 10 mg/L; 2) performing first zinc powder replacement in zinc-containing solution to carry out a first period of purification to at least remove copper and cadmium; 3) carrying out solid-liquid separation to filter the zinc-containing solution containing solid impurities of copper and cadmium, where filtering time is controlled to be within 60 minutes and filter precision is controlled to be below 10 µm;
4) carrying out a second period of purification on the zinc-containing solution after the solid-liquid separation for filtration to at least remove cobalt and nickel; and 5) carrying out solid-liquid separation to filter the zinc-containing solution containing solid impurities of cobalt and nickel, so as to obtain a fresh solution and a filtration residue, wherein in the filtration residue, the weight ratio of the solid cadmium to the solid zinc is less than 1 x10-5, and wherein the step 1) is implemented by performing cross-flow membrane filtration on the neutral leachate or the supernatant, and for the step 3) and the step 4), at least the step 3) adopts a terminal membrane filtration.
4) carrying out a second period of purification on the zinc-containing solution after the solid-liquid separation for filtration to at least remove cobalt and nickel; and 5) carrying out solid-liquid separation to filter the zinc-containing solution containing solid impurities of cobalt and nickel, so as to obtain a fresh solution and a filtration residue, wherein in the filtration residue, the weight ratio of the solid cadmium to the solid zinc is less than 1 x10-5, and wherein the step 1) is implemented by performing cross-flow membrane filtration on the neutral leachate or the supernatant, and for the step 3) and the step 4), at least the step 3) adopts a terminal membrane filtration.
3. The purification method of zinc-containing solution according to claim 2, wherein the filtration residue obtained in the step 5) serves as a zinc powder raw material used for performing the zinc powder replacement in the step 2).
4. The purification method of zinc-containing solution according to claim 2, wherein a second zinc powder replacement is performed on the zinc-containing solution to carry out the second period of purification and to at least remove cobalt and nickel.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210137907.3 | 2012-05-07 | ||
| CN201210137907.3A CN102808083B (en) | 2012-05-07 | 2012-05-07 | Cadmium removing process for use in zinc liquid purification and zinc liquid purifying method |
| PCT/CN2012/079545 WO2013166789A1 (en) | 2012-05-07 | 2012-08-02 | Cadmium removing process in zinc-containing solution purification and purification method of zinc-containing solution |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2872927A1 CA2872927A1 (en) | 2013-11-14 |
| CA2872927C true CA2872927C (en) | 2017-07-11 |
Family
ID=47231952
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA2872927A Active CA2872927C (en) | 2012-05-07 | 2012-08-02 | Cadmium removing process in zinc-containing solution purification and purification method of zinc-containing solution |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP6114381B2 (en) |
| KR (1) | KR101939433B1 (en) |
| CN (1) | CN102808083B (en) |
| CA (1) | CA2872927C (en) |
| WO (1) | WO2013166789A1 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103773958B (en) * | 2014-01-28 | 2015-11-25 | 白银有色集团股份有限公司 | A kind of method for removing cadmium |
| CN108842071B (en) * | 2018-05-31 | 2020-07-24 | 西北矿冶研究院 | Method for improving purification efficiency of zinc hydrometallurgy |
| CN110699556A (en) * | 2019-08-23 | 2020-01-17 | 白银有色集团股份有限公司 | Method for deep purification and cadmium and cobalt removal of supernatant in zinc hydrometallurgy |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03219799A (en) * | 1990-01-24 | 1991-09-27 | Toshiba Corp | Sound effect equipment |
| JPH05171310A (en) * | 1991-12-25 | 1993-07-09 | Mitsubishi Materials Corp | Zinc smelting method by reducing roasting |
| KR20000052340A (en) * | 1999-01-23 | 2000-08-25 | 이호인 | Zine collecting method from steel powder containing zinc ferrite |
| CN1125883C (en) * | 1999-07-09 | 2003-10-29 | 水口山有色金属有限责任公司 | High-purity zinc and its preparing process |
| JP3794260B2 (en) | 2000-10-30 | 2006-07-05 | 太平洋セメント株式会社 | Waste disposal method |
| JP2006075821A (en) * | 2004-08-09 | 2006-03-23 | Kochi Univ | Method for removing and recovering heavy metal in soil |
| JP4180036B2 (en) | 2004-09-24 | 2008-11-12 | 日鉱金属株式会社 | Cadmium leachate treatment method |
| CN100460326C (en) * | 2006-03-15 | 2009-02-11 | 南京九思高科技有限公司 | Method of refining salt by membrane filtration |
| CN101289706A (en) * | 2008-06-16 | 2008-10-22 | 中南大学 | Process for preparing electrolytic zinc form treated zinc oxide ore or zinc oxide secondary resource |
| CN101713031B (en) | 2009-10-26 | 2011-05-18 | 德阳市南邡有色金属有限公司 | Method for removing impurities by oxidation in process of zinc hydrometallurgy |
| CN101994005B (en) * | 2010-12-10 | 2012-08-15 | 株洲冶炼集团股份有限公司 | Method for purifying zinc sulfate solution and removing cobalt by using arsenic ash lixivium |
-
2012
- 2012-05-07 CN CN201210137907.3A patent/CN102808083B/en active Active
- 2012-08-02 CA CA2872927A patent/CA2872927C/en active Active
- 2012-08-02 KR KR1020147032034A patent/KR101939433B1/en active IP Right Grant
- 2012-08-02 WO PCT/CN2012/079545 patent/WO2013166789A1/en active Application Filing
- 2012-08-02 JP JP2015510607A patent/JP6114381B2/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| JP6114381B2 (en) | 2017-04-12 |
| CN102808083A (en) | 2012-12-05 |
| KR20150007315A (en) | 2015-01-20 |
| KR101939433B1 (en) | 2019-01-16 |
| WO2013166789A1 (en) | 2013-11-14 |
| JP2015516033A (en) | 2015-06-04 |
| CA2872927A1 (en) | 2013-11-14 |
| CN102808083B (en) | 2014-12-10 |
| WO2013166789A8 (en) | 2014-07-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103882234B (en) | A kind of method neodymium iron boron greasy filth being prepared into regeneration NdFeB magnetic powder | |
| CN103924267B (en) | A kind of method preparing Spongy Cadmium under micro-function of current | |
| JP5250683B2 (en) | Recovery method of valuable metals from Pb-free waste solder | |
| CN104386860B (en) | A kind of method processing complexation of metal ions waste water | |
| CA2872927C (en) | Cadmium removing process in zinc-containing solution purification and purification method of zinc-containing solution | |
| CN101302585A (en) | Method for preparing high-purity cobalt | |
| Jin et al. | Electrolytic recovery of bismuth and copper as a powder from acidic sulfate effluents using an emew® cell | |
| CN101122032A (en) | One-step producing technique for high-purity gold | |
| CN105441974B (en) | A kind of method for producing electro deposited nickel | |
| CN104694751B (en) | A kind of method of removing chloride ion in leachate from zinc hydrometallurgy | |
| CN102676845B (en) | Filter residue obtained after purifying zinc liquid and preparation method of filter residue | |
| CN101538721A (en) | Method for preparing high-purity cobalt | |
| CN104726894A (en) | Gallium recycling method | |
| JP6365395B2 (en) | Method for producing nickel sulfate | |
| JP5628610B2 (en) | Indium recovery method | |
| CN108359804A (en) | A method of it being enriched with tungsten tantalum hafnium from high-temperature alloy waste material | |
| Xiao et al. | Role of trivalent antimony in the removal of As, Sb, and Bi impurities from copper electrolytes | |
| CN109576494A (en) | The method for preparing sodium sulphate using Treatment of Metal Surface waste | |
| CN100588746C (en) | Non-copper ionic-silver electrolyzation | |
| CN106319564B (en) | A kind of method of the method and electrolytic metal ion of metallic copper, Treatment of Copper ion waste water | |
| CN111286609A (en) | Method for separating and purifying lead, zinc, cadmium and copper based on ammonium complex system | |
| KR101619346B1 (en) | Recovering method of tin metal using tin extracts | |
| CN113930807B (en) | Method for preparing copper-arsenic alloy by pulse electrodeposition | |
| CN106917112B (en) | A kind of method of zinc-ammonia-ammonium salt solution system replacement deposition sponge copper powder | |
| CN102796871B (en) | Method for treating cast of lead anode plate in electro-deposit copper |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request |
Effective date: 20150811 |