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
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- 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
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- 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
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- C—CHEMISTRY; METALLURGY
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- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
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- 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
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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.
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