CN112337433A - Preparation method and application of renewable cadmium removal agent and regeneration method - Google Patents
Preparation method and application of renewable cadmium removal agent and regeneration method Download PDFInfo
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3078—Thermal treatment, e.g. calcining or pyrolizing
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
- B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
- B01J20/3234—Inorganic material layers
- B01J20/3236—Inorganic material layers containing metal, other than zeolites, e.g. oxides, hydroxides, sulphides or salts
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/34—Regenerating or reactivating
- B01J20/3441—Regeneration or reactivation by electric current, ultrasound or irradiation, e.g. electromagnetic radiation such as X-rays, UV, light, microwaves
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- 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
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- 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
- C22B3/24—Treatment or purification of solutions, e.g. obtained by leaching by physical processes, e.g. by filtration, by magnetic means, or by thermal decomposition by adsorption on solid substances, e.g. by extraction with solid resins
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- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/22—Electroplating: Baths therefor from solutions of zinc
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The invention discloses a preparation method of a renewable cadmium removing agent, which comprises the steps of dipping activated carbon in a zinc nitrate solution, and then carrying out reduction roasting to obtain the renewable cadmium removing agent. The invention also discloses application of the renewable cadmium removing agent in cadmium purification and removal of zinc leachate in zinc hydrometallurgy industry, the cadmium removing agent is added into the zinc leachate, and the zinc leachate is heated, stirred, reacted and filtered to complete the purification and removal of cadmium in the zinc leachate. The regeneration method comprises the step of electrolyzing the cadmium removing agent subjected to cadmium removal as a cathode, a zinc sheet as an anode and zinc sulfate solution as electrolyte to obtain the regenerated cadmium removing agent. The cadmium removing agent disclosed by the invention is high in cadmium removing efficiency, and can reduce the zinc consumption in unit cadmium removing process in the zinc leachate cadmium removing process in the zinc hydrometallurgy industry. The cadmium removing agent is easy to recycle and regenerate, the cadmium removing efficiency of the cadmium removing agent is still higher than 90% after 6 times of circulation, and the cadmium removing operation cost is greatly reduced.
Description
Technical Field
The invention belongs to the field of environmental purification treatment, and particularly relates to a preparation method, application and a regeneration method of a renewable cadmium removal agent for deep removal of cadmium in zinc leachate in the zinc hydrometallurgy industry.
Background
Along with the increasing depletion of high-grade zinc concentrate, the recovery of zinc from low-grade complex zinc concentrate or zinc secondary resource becomes an important way for guaranteeing the zinc requirement of China gradually. The conventional low-grade complex zinc concentrate and zinc secondary resource are usually accompanied by a large amount of cadmium, which inevitably enters the leaching solution along with zinc in the leaching process to form cadmium-containing zinc leaching solution. Generally, the cadmium content in low-grade complex zinc concentrate and zinc secondary resource leachate is higher, and is usually more than 0.8 g/L. However, cadmium in the solution can cause serious harm to the subsequent zinc electrolysis, so how to economically and efficiently purify cadmium from the zinc leachate becomes a problem to be solved urgently.
The traditional cadmium removing method can be mainly divided into three methods of adsorption cadmium removal, hydrolysis precipitation cadmium removal and replacement cadmium removal. The method for adsorbing and removing cadmium mainly utilizes the strong affinity of adsorbents such as resin, sulfide and the like to cadmium, thereby realizing the adsorption and removal of the cadmium. The zinc concentration in the zinc hydrometallurgy leaching solution is very high, the deep purification of cadmium in the high zinc solution is difficult to realize by the cadmium adsorption removal method, the adsorbent used by the adsorption method is difficult to recycle, and the formed cadmium-containing waste adsorbent is difficult to treat, and the problems limit the application of the adsorption method in the field of cadmium purification of the zinc hydrometallurgy leaching solution. The hydrolysis precipitation for removing cadmium utilizes the characteristic that cadmium ions are easy to form insoluble and stable cadmium hydroxide precipitate in an alkaline system, and the cadmium is removed by adjusting the pH value of the leaching solution. However, in the process of adjusting the pH, when the concentration of zinc is far higher than that of cadmium, zinc in the solution is precipitated preferentially by cadmium, so that the loss of zinc is caused, and the deep removal of cadmium cannot be realized. The displacement cadmium removal method is to replace active metal with cadmium ions in a solution so as to realize the removal of cadmium. For the zinc hydrometallurgy industry, the replacement method is the most common method, and zinc powder is generally adopted for replacing and removing cadmium, but excessive zinc powder needs to be added in the replacement process, so that the cadmium removal cost is greatly increased.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the defects and shortcomings in the background technology and providing a preparation method, application and a regeneration method of a renewable cadmium removal agent so as to reduce the purification and removal cost of cadmium.
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
a preparation method of a renewable cadmium removing agent comprises the steps of dipping activated carbon in a zinc nitrate solution, and then carrying out reduction roasting to obtain the renewable cadmium removing agent.
In the preparation method, the concentration of the zinc nitrate solution is preferably 0.1-0.3 mol/L, and the dipping time is preferably 30-60 min.
In the above preparation method, preferably, the particle size of the activated carbon is less than 1 mm; the volume ratio of the activated carbon to the zinc nitrate solution in the dipping treatment process is 1: (2-5).
In the preparation method, preferably, the reduction roasting temperature is 500-700 ℃, and the roasting time is 0.5-2 h.
In the above preparation method, preferably, the atmosphere in the reductive calcination is hydrogen or carbon monoxide; wherein the volume concentration of the hydrogen is 5-10%, and the volume concentration of the carbon monoxide is 10-40%.
In the preparation method, the cadmium removing agent is preferably prepared by taking activated carbon as a matrix, wherein the activated carbon matrix is loaded with metal zinc.
The preparation method of the cadmium removing agent mainly comprises a dipping process and a reduction roasting process, wherein in the dipping process of a zinc nitrate solution, zinc in the solution is adsorbed by various functional groups (hydroxyl, carboxyl and the like) on the surface of active carbon to form zinc-containing active carbon, and the zinc-containing active carbon can form a large amount of simple substance zinc particles (generally the particle size is not more than 1 micron) on the surface of the active carbon in situ through the reduction roasting and is uniformly fixed in the aperture of the active carbon to form the cadmium removing agent. In the cadmium removing agent, as the activated carbon has the characteristics of porous structure and large specific surface area, cadmium ions in the leaching solution can more easily and quickly carry out replacement reaction with zinc of the cadmium removing agent, and the cadmium removing efficiency is greatly improved. In addition, the zinc particles are uniformly fixed in porous activated carbon pore canals, so that the zinc particles can be fully contacted with cadmium in a solution, the defect of high zinc powder consumption caused by zinc side reaction due to low local cadmium concentration around the zinc powder in the conventional zinc powder replacement process is avoided, and the zinc consumption of unit cadmium removal is greatly reduced.
As a general inventive concept, the invention also provides an application of the renewable cadmium removing agent prepared by the preparation method in the purification and removal of cadmium in zinc leachate in the zinc hydrometallurgy industry.
In the above application, preferably, the volume ratio of the cadmium removing agent to the zinc leaching solution is (0.02-0.05): 1.
in the application, preferably, the heating temperature is 40-60 ℃, the stirring speed is 200-500 r/min, and the reaction time is 30-45 min.
As a general inventive concept, the invention also provides a regeneration method of the cadmium removing agent, which takes the cadmium removing agent after cadmium removal as a cathode, a zinc sheet as an anode and zinc sulfate solution as electrolyte to carry out electrolysis to obtain the regenerated cadmium removing agent.
In the regeneration method, the concentration of the zinc sulfate solution is preferably 20-40 g/L, and the current density is preferablyIs 100 to 180A/m3The electrolysis time is 60-120 s.
In the cadmium purification and removal process, a layer of cadmium metal is covered on the surface of zinc particles along with the replacement process, so that the cadmium removal efficiency of the cadmium removal agent is reduced. The cadmium removing agent after cadmium removal is used as a cathode, elemental zinc is used as an anode, zinc sulfate solution is used as electrolyte, and the elemental zinc can be deposited in situ on the surfaces of the particles with the surfaces covered with cadmium by controlling the electrolysis time and the current density, so that the regeneration of the cadmium removing agent is realized.
Compared with the prior art, the invention has the advantages that:
(1) the cadmium removing agent disclosed by the invention is high in cadmium removing efficiency, and can reduce the zinc consumption in unit cadmium removing process in the zinc leachate cadmium removing process in the zinc hydrometallurgy industry.
(2) The cadmium removing agent has the advantages of simple preparation process, wide raw material source and low cost.
(3) The cadmium removing agent is easy to recycle and regenerate, the cadmium removing efficiency of the cadmium removing agent is still higher than 90% after 6 times of circulation, and the cadmium removing operation cost is greatly reduced.
Drawings
FIG. 1 is the adsorption capacity of the regenerable cadmium removal agent prepared in example 1 of the present invention.
FIG. 2 is the adsorption capacity of the regenerable cadmium removal agent prepared in example 2 of the present invention.
FIG. 3 is the adsorption capacity of the regenerable cadmium removal agent prepared in example 3 of the present invention.
FIG. 4 is the adsorption capacity of the regenerable cadmium removal agent prepared in example 4 of the present invention.
FIG. 5 is the adsorption capacity of the regenerable cadmium removal agent prepared in example 5 of the present invention.
Detailed Description
In order to facilitate an understanding of the invention, the invention will be described more fully and in detail below with reference to the accompanying drawings and preferred embodiments, but the scope of the invention is not limited to the specific embodiments below.
Unless otherwise defined, all terms of art used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention.
Unless otherwise specifically stated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be prepared by existing methods.
Example 1:
the preparation method of the renewable cadmium removal agent comprises the following steps:
(1) crushing commercially available commercial activated carbon, and then sieving to ensure that the granularity of the activated carbon is less than 1 mm; then zinc nitrate solutions with the concentrations of 0.05mol/L, 0.1mol/L, 0.2mol/L, 0.3mol/L and 0.4mol/L are respectively prepared;
(2) respectively taking 5 parts of crushed and sieved activated carbon with the volume of 100mL, respectively adding the activated carbon into 200mL of zinc nitrate solutions with different concentrations prepared in the step (1), fully stirring and soaking for 45 min;
(3) and (3) filtering the mixed solution obtained in the step (2), drying the activated carbon, and respectively carrying out reduction roasting on the dried activated carbon in CO gas with the volume concentration of 15%, wherein the roasting temperature is 600 ℃, and the roasting time is 1h, so as to obtain 5 parts of the renewable cadmium removing agent.
Preparing a simulated zinc leaching solution (the concentration of zinc sulfate is 150g/L, and the concentration of cadmium is 1 g/L). The cadmium removing agent prepared in the embodiment with the volume of 20mL is taken, 5 parts of the cadmium removing agent are respectively added into 1L of simulated zinc leaching solution, the mixture is stirred at the rotating speed of 250r/min for 30min to carry out reaction, and the temperature is maintained at 50 ℃ in the whole reaction process. After the reaction is completed, filtering and separating the cadmium removal agent, and detecting the content of cadmium in the solution to obtain the cadmium removal efficiency, wherein the specific experimental result is shown in fig. 1. From the figure, it can be known that the too low and too high concentration of zinc nitrate in the dipping process of the cadmium removing agent preparation is not good for the cadmium removing agent performance, the too low and too high concentration of zinc nitrate is not good for the zinc particles to form uniform distribution on the cadmium removing agent, and when the optimal concentration of zinc nitrate is 0.1-0.3 mol/L, the removal efficiency of the prepared cadmium removing agent is higher than 94%.
Example 2:
the preparation method of the renewable cadmium removal agent comprises the following steps:
(1) crushing commercial activated carbon sold in the market, and then sieving to ensure that the granularity of the activated carbon is less than 1 mm; then preparing 0.2mol/L zinc nitrate solution with a certain volume;
(2) taking 6 parts of crushed and sieved activated carbon with the volume of 100mL, respectively adding 200mL of the zinc nitrate solution prepared in the step (1), fully stirring and respectively soaking for 15min, 30min, 45min, 60min, 75min and 90 min;
(3) and (3) filtering the mixed solution reacted in the step (2), drying the impregnated activated carbon, and reducing and roasting the dried activated carbon by using CO gas with the volume concentration of 15%, wherein the roasting temperature is 600 ℃, and the roasting time is 1h, so that the renewable cadmium removing agent is obtained.
Preparing a simulated zinc leaching solution (the concentration of zinc sulfate is 150g/L, and the concentration of cadmium is 1 g/L). The cadmium removing agent prepared in this example with a volume of 20mL in total of 6 parts is taken, and is added into 1L of simulated zinc leaching solution respectively, the stirring is carried out for 30min at a rotating speed of 250r/min, the temperature is maintained at 50 ℃ in the whole reaction process, after the reaction, the cadmium removing agent is filtered and separated, the content of cadmium in the solution is detected, the cadmium removing efficiency is obtained, and the specific experimental result is shown in fig. 2. It can be seen from the figure that, when the dipping time of the zinc nitrate in the preparation process of the cadmium removing agent is 15min, the cadmium removing efficiency of the cadmium removing agent is only 76.2%, the cadmium removing efficiency is improved to more than 94.01% after the dipping time is continuously increased to 30min, and the cadmium removing efficiency is not changed greatly and is maintained at about 95% after the dipping time is continuously increased. And comprehensively considering economy and efficiency, and selecting the dipping time to be 30-45 min.
Example 3:
the preparation method of the renewable cadmium removal agent comprises the following steps:
(1) crushing commercially available commercial activated carbon, and then sieving to ensure that the granularity of the activated carbon is less than 1 mm; then preparing 0.2mol/L zinc nitrate solution with a certain volume;
(2) taking 6 parts of crushed and sieved activated carbon with the volume of 100mL, respectively adding the activated carbon into 6 parts of 200mL of zinc nitrate solution prepared in the step (1), uniformly stirring and soaking for 30 min;
(3) and (3) filtering the mixed solution reacted in the step (2), drying the impregnated activated carbon, and reducing and roasting the dried activated carbon by using CO gas with the volume concentration of 15%, wherein the roasting temperatures are 300 ℃, 400 ℃, 500 ℃, 600 ℃, 700 ℃ and 800 ℃ respectively, and the roasting time is 1h, so that the renewable cadmium removing agent is obtained.
Preparing a simulated zinc leaching solution (the concentration of zinc sulfate is 150g/L, and the concentration of cadmium is 1 g/L). The cadmium removing agent prepared under different conditions in the embodiment with the volume of 20mL is taken to be 6 parts, the 6 parts are respectively added into 1L of simulated zinc leaching solution, the stirring is carried out for 30min at the rotating speed of 250r/min, the temperature in the whole reaction process is maintained at 50 ℃, after the reaction is finished, the cadmium removing agent is filtered and separated, the content of cadmium in the solution is detected, and the cadmium removing efficiency is obtained, and the specific experimental result is shown in figure 3. As can be seen from the figure, when the reduction roasting temperature is low, the cadmium removal efficiency is low, and at this time, the zinc supported on the activated carbon is difficult to be reduced into zinc fine particles. When the reduction temperature is increased to 500 ℃, the cadmium removal efficiency is rapidly improved to more than 90 percent, and the cadmium removal efficiency is kept at a higher level when the temperature is continuously increased. When the reduction roasting temperature reaches 800 ℃, the removal efficiency of cadmium is reduced to 82.1%, and zinc loaded on the activated carbon is volatilized to a gas phase possibly due to overhigh temperature, so that the formation amount of zinc particles is reduced. Therefore, the reduction temperature is selected to be 500-700 ℃.
Comparative example 1:
20g of each cadmium removing agent prepared in the example 3 at the reduction temperature of 600 ℃ and 20g of commercial zinc powder are respectively taken and added into 1L of prepared simulated zinc leaching solution (the concentration of zinc sulfate is 150g/L, the concentration of cadmium is 1g/L) and the temperature of the whole reaction process is maintained at 50 ℃ at the rotation speed of 250 r/min. And (3) respectively taking a small amount of leachate at different reaction times, filtering and detecting the content of cadmium in the solution to obtain the cadmium removal efficiency at different reaction times, wherein the specific experimental results are shown in table 1.
TABLE 1 cadmium removal efficiency at different reaction times
| Reaction time (min) | 5 | 15 | 30 | 45 | 60 | 75 | 90 |
| Cadmium removal efficiency (%) of zinc powder | 25.36 | 56.33 | 79.47 | 86.56 | 95.43 | 95.74 | 95.63 |
| Cadmium removal efficiency of cadmium removing agent (%) | 32.19 | 76.21 | 93.42 | 95.23 | 95.53 | 95.68 | 95.36 |
As can be seen from Table 1, the cadmium removing agent of the present invention has a higher cadmium removing rate than zinc powder. For example, the cadmium removing efficiency of the cadmium removing agent is obviously higher than that of zinc powder when the reaction time is 30 min. In addition, the mass fraction of zinc in the cadmium removing agent is usually between 8 and 15 percent, and under the same mass condition, the cadmium removing amount of unit zinc on the cadmium removing agent is larger, namely the cadmium removing utilization rate of zinc is higher. Compared with the traditional zinc powder replacement cadmium removal, the cadmium removal agent has excellent cadmium removal performance.
Example 4:
the invention relates to a regeneration method of a cadmium removing agent, which comprises the following steps:
20g of the cadmium removing agent used in example 2 (the regenerated cadmium removing agent prepared by immersing in a zinc nitrate solution for 45min and the cadmium removing agent studied by a cadmium removing test in a simulated zinc leaching solution) was placed in a carbon net and used as a cathode. Taking a zinc sheet as an anode and zinc sulfate solution as electrolyte to carry out electrodeposition, wherein the concentration of the zinc sulfate electrolyte adopted in the electrodeposition process is 30g/L, and the current density is 150A/m3The electrolysis time is respectively set to 30s, 60s, 90s, 120s, 150s and 180s, and the regenerated cadmium removing agent under different electrolysis times is obtained.
Preparing a simulated zinc leaching solution (the concentration of zinc sulfate is 150g/L, and the concentration of cadmium is 1 g/L). 6 portions of the regenerated cadmium removal agent prepared under different conditions in the embodiment with the volume of 20mL are respectively added into 1L of simulated zinc leaching solution and stirred for 30min at the rotating speed of 250r/min, and the temperature in the whole reaction process is maintained at 50 ℃. After the reaction is completed, filtering and separating the cadmium removal agent, and detecting the content of cadmium in the solution to obtain the cadmium removal efficiency, wherein the specific experimental result is shown in fig. 4. It can be seen from the figure that when the electrolysis time is short, the cadmium removal performance of the regenerated cadmium removal agent is not high, and when the electrolysis time is continuously increased to 60s, the cadmium removal efficiency of the regenerated cadmium removal agent is stabilized to be more than 91%, and when the electrolysis time exceeds 120s, the cadmium removal efficiency begins to decline. This is probably because too short electrolysis time is not favorable for the complete deposition of zinc on the cadmium removing agent, and too long electrolysis time causes the excessive growth of zinc particles and is also not favorable for the removal of cadmium, so the optimal electrolysis time is 60-120 s.
Example 5:
the invention relates to a regeneration method of a cadmium removing agent, which comprises the following steps:
20g of the cadmium removing agent used in example 2 (the regenerated cadmium removing agent prepared by immersing in a zinc nitrate solution for 45min and the cadmium removing agent studied by a cadmium removing test in a simulated zinc leaching solution) was placed in a carbon net and used as a cathode. Taking a zinc sheet as an anode and zinc sulfate solution as electrolyte to carry out electrodeposition, wherein the concentration of the zinc sulfate electrolyte adopted in the electrodeposition process is 30g/L, and the current density is 150A/m3And the electrolysis time is 90s, and the regenerated cadmium removing agent is obtained.
Preparing a simulated zinc leaching solution (the concentration of zinc sulfate is 150g/L, and the concentration of cadmium is 1 g/L). Adding a regenerated cadmium removal agent with the volume of 20mL into 1L of simulated zinc leaching solution, stirring at the rotating speed of 250r/min for 30min, and maintaining the temperature at 50 ℃ in the whole reaction process. And after the reaction is finished, filtering and separating the cadmium removing agent, and detecting the content of cadmium in the solution to obtain the cadmium removing efficiency.
The regenerated cadmium removing agent of the embodiment is repeatedly regenerated for 4 times again, and the cadmium removing effect of the regenerated cadmium removing agent under the condition of 5 cycles is finally obtained, and the specific result is shown in fig. 5. As can be seen from the figure, under the condition of 5 regeneration cycles, the cadmium removal efficiency of the cadmium removal agent is stabilized to be more than 90%, which shows that the cadmium removal agent has excellent cycle regeneration performance.
Claims (10)
1. A preparation method of a renewable cadmium removal agent is characterized in that activated carbon is dipped in a zinc nitrate solution and then is subjected to reduction roasting to obtain the renewable cadmium removal agent.
2. The method according to claim 1, wherein the concentration of the zinc nitrate solution is 0.1 to 0.3mol/L, and the dipping time is 30 to 60 min.
3. The method of claim 1, wherein the activated carbon has a particle size of less than 1 mm; the volume ratio of the activated carbon to the zinc nitrate solution in the dipping treatment process is 1: (2-5).
4. The method according to any one of claims 1 to 3, wherein the reduction roasting temperature is 500 to 700 ℃ and the roasting time is 0.5 to 2 hours.
5. The production method according to any one of claims 1 to 3, wherein an atmosphere of the reductive calcination is hydrogen or carbon monoxide.
6. The preparation method according to any one of claims 1 to 3, wherein the obtained cadmium removing agent is activated carbon as a matrix, and metal zinc is loaded in the activated carbon matrix.
7. The application of the renewable cadmium removing agent prepared by the preparation method of any one of claims 1 to 6 in cadmium purification and removal of zinc leachate in the zinc hydrometallurgy industry is characterized in that the cadmium removing agent is added into the zinc leachate, heated and stirred for reaction, and filtered to complete the purification and removal of cadmium in the zinc leachate.
8. The use of claim 7, wherein the volume ratio of the cadmium removal agent to the zinc leachate is (0.02-0.05): 1.
9. the use according to claim 7, wherein the heating temperature is 40-60 ℃, the stirring rate is 200-500 r/min, and the reaction time is 30-45 min.
10. The regeneration method of the cadmium removing agent used in any one of claims 7 to 9, characterized in that the cadmium removing agent is used as a cathode, a zinc sheet is used as an anode, and a zinc sulfate solution is used as an electrolyte, and the regeneration cadmium removing agent is obtained by electrolysis; wherein the concentration of the zinc sulfate solution is 20-40 g/L, and the current density is 100-180A/m3The electrolysis time is 60 to120s。
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