CN114717421A - Method for comprehensively recycling zinc and cadmium from cadmium scum - Google Patents
Method for comprehensively recycling zinc and cadmium from cadmium scum Download PDFInfo
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- CN114717421A CN114717421A CN202210447971.5A CN202210447971A CN114717421A CN 114717421 A CN114717421 A CN 114717421A CN 202210447971 A CN202210447971 A CN 202210447971A CN 114717421 A CN114717421 A CN 114717421A
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- cadmium
- ore pulp
- dross
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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
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
- C22B7/007—Wet processes by acid leaching
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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
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/005—Preliminary treatment of scrap
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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
- C22B17/00—Obtaining cadmium
- C22B17/04—Obtaining cadmium by wet processes
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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
- C22B19/30—Obtaining zinc or zinc oxide from metallic residues or scraps
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The invention discloses a method for comprehensively recycling zinc and cadmium from cadmium dross, which relates to the technical field of hydrometallurgy and comprises the following steps: acid washing cadmium scum, solid-liquid separation, leaching cadmium scum, filtering and recovering; the method comprises the steps of adopting a high-temperature water washing-physical screening-manganese dioxide oxidation-hot acid leaching method for treatment, washing cadmium scum generated by a cadmium preparation system at high temperature to obtain water-washed dissolved ore pulp, obtaining liquid ore pulp and blocky objects through physical screening, carrying out manganese dioxide oxidation and high-temperature leaching on the liquid ore pulp to ensure that zinc and cadmium in the liquid are leached into the liquid to the maximum extent, returning to a corresponding wet process, ensuring that valuable metal resources such as zinc, cadmium and the like are recycled, effectively utilizing the waste cadmium scum, having good economic benefit, and reducing the pollution to the environment caused by stacking and storing the cadmium scum through recycling of the cadmium scum.
Description
Technical Field
The invention relates to the technical field of hydrometallurgy, in particular to a method for comprehensively recycling zinc and cadmium by cadmium dross.
Background
Cadmium dross is used as a hazardous waste residue produced in a zinc hydrometallurgy purification process, and mainly comprises cadmium, zinc and sodium, wherein the cadmium is mainly clamped in the cadmium dross in the form of cadmium particles, cadmium blocks and cadmium oxide, the zinc and the sodium mainly exist in the form of sodium zincate, and valuable metals such as zinc, cadmium and the like account for more than 55 percent. If the cadmium scum is stockpiled, not only the resource loss and waste are caused, but also certain pollution is caused to the environment, so that the cadmium scum needs to be comprehensively recycled.
Disclosure of Invention
The invention aims to: in order to solve the technical problem, the invention provides a method for comprehensively recycling zinc and cadmium from cadmium dross.
The invention specifically adopts the following technical scheme for realizing the purpose: a method for comprehensively recycling zinc and cadmium from cadmium dross comprises the following steps:
step one, acid pickling of cadmium dross: adding cadmium dross produced by a cadmium mass smelting furnace into hot water, wherein the volume ratio of the cadmium dross to the hot water is 1:4-5, adding a small amount of concentrated sulfuric acid into the hot water, fully reacting and dissolving the concentrated sulfuric acid and the cadmium dross, and continuously stirring to fully dissolve the concentrated sulfuric acid and the cadmium dross to form ore pulp;
step two, solid-liquid separation: adding clear water into the ore pulp for water washing, filtering the water-washed ore pulp to obtain liquid ore pulp and a block, and returning the block to the cadmium mass smelting furnace to produce crude cadmium;
step three, cadmium scum leaching: adding manganese dioxide into the liquid ore pulp for oxidation, simultaneously adding concentrated sulfuric acid for leaching, controlling reaction conditions, continuously detecting the color and the pH value of the liquid ore pulp, supplementing the manganese dioxide and the concentrated sulfuric acid in time to ensure that the reaction is fully performed, and reacting the manganese dioxide with zinc and cadmium in the ore pulp to obtain leachate containing zinc and cadmium in ionic forms;
step four, filtering and recycling: and filtering the leaching solution to obtain filter residue and filtrate, returning the filter residue to the third copper-cadmium residue leaching procedure for continuous leaching, and returning the filtrate to the cadmium preparation procedure to recover zinc and cadmium.
Preferably, the volume ratio of the ore pulp to the clear water added in the step two is 1: 4-5.
Preferably, the reaction conditions in the third step comprise the temperature of the liquid ore pulp, the leaching time and the pH value.
Further, the temperature is 80-90 ℃, the leaching time is 3-4h, and the pH value is 1.5-3.0.
The invention has the following beneficial effects:
1. the method comprises the following steps of (1) treating by adopting a high-temperature water washing-physical screening-manganese dioxide oxidation-hot acid leaching method, washing cadmium scum generated by a cadmium preparation system at high temperature to obtain water-washed dissolved ore pulp, carrying out physical screening to obtain liquid ore pulp and lumps, carrying out manganese dioxide oxidation and high-temperature leaching on the liquid ore pulp, leaching zinc and cadmium in the liquid into the liquid to the maximum extent, returning to a corresponding wet process, ensuring that valuable metal resources such as zinc, cadmium and the like are recycled, reducing resource waste and having good economic benefit;
2. the method for comprehensively recycling zinc and cadmium by using cadmium scum reduces the stacking and storage of the cadmium scum, further reduces the pollution to the environment and has good social benefit.
Description of the drawings:
FIG. 1 is a process flow diagram of the present invention
Detailed Description
The present invention will now be described in detail with reference to the drawings and specific embodiments, wherein the exemplary embodiments and descriptions of the present invention are provided to explain the present invention without limiting the invention thereto.
Referring to fig. 1, the cadmium dross of the present invention comprises the following main components by weight: zn: 20-30%, Cd: 30 to 40 percent.
Example 1
In the method for comprehensively recycling zinc and cadmium from cadmium dross, the cadmium dross comprises the following main components in percentage by weight: zn: 23.47%, Cd: 39.52 percent.
(1) Taking 450 g of cadmium dross, adding water into the cadmium dross according to a liquid-solid volume ratio of 5:1, heating the cadmium dross to 70 ℃ of water, simultaneously slowly adding concentrated sulfuric acid, stopping adding concentrated sulfuric acid when the pH value of the solution is less than or equal to 4.5, continuing the reaction, supplementing the concentrated sulfuric acid until the pH value is 4.5 when the pH value of the solution is higher than 5.0, stopping adding acid, repeating the adding process of the concentrated sulfuric acid, finishing the acid washing operation of the cadmium dross when the pH value of ore pulp is stabilized between 4.5 and 5.0 for 30min, wherein the end-point pH value of the ore pulp is 4.5, and the whole acid washing process lasts for 1.0 h; the purpose of this process is to make the soluble matters such as zinc, sodium and cadmium oxide in cadmium dross go into solution as much as possible.
(2) And (2) physically separating the ore pulp dissolved in the water washing step (1) into liquid ore pulp and block-shaped materials, wherein the liquid ore pulp is subjected to subsequent reaction, and the block-shaped materials are returned to a cadmium mass smelting furnace to produce crude cadmium.
(3) Controlling the temperature of the ore pulp in the step (2) to 85 ℃, simultaneously slowly adding manganese dioxide and concentrated sulfuric acid for oxidation leaching, stopping adding concentrated sulfuric acid when the pH value of the solution is less than or equal to 1.5, continuing the reaction, supplementing oxidants of manganese dioxide and concentrated sulfuric acid until the pH value is 1.5 when the pH value of the solution is higher than 3.0, stopping adding acid, repeating the adding process of concentrated sulfuric acid, finishing the acid washing operation of cadmium dross when the pH value of the ore pulp is stabilized between 1.5 and 3.0 for 30min, wherein the end-point pH value of the ore pulp is 2.5, and the whole acid washing process lasts for 3.0 h; in the reaction process, manganese dioxide and concentrated sulfuric acid which are oxidants are consumables, so that in the experimental process, the conditions of the color and the pH value of the liquid need to be continuously detected and supplemented in time to ensure that the reaction is fully carried out.
(4) And (3) filtering the leachate obtained in the step (3), continuously leaching the filter residue in a copper-cadmium residue leaching process, and recovering zinc and cadmium from the filtrate in a cadmium preparation process.
The solution comprises the following main components: zn: 38.74g/l, Cd: 67.81g/l, Mn: 25.12g/l, acidity 8.66g/l, slag component Zn: 2.97%, Cd: 8.97 percent
Example 2
In the method for comprehensively recycling zinc and cadmium from cadmium dross, the cadmium dross comprises the following main components in percentage by weight: zn: 29.92%, Cd: 34.82 percent.
(1) Taking 320 g of cadmium dross, adding water into the cadmium dross according to a liquid-solid volume ratio of 5:1, heating the cadmium dross to 70 ℃ of water, simultaneously slowly adding concentrated sulfuric acid, stopping adding concentrated sulfuric acid when the pH value of the solution is less than or equal to 4.5, continuing the reaction, supplementing concentrated sulfuric acid when the pH value of the solution is higher than 5.0 until the pH value is 4.5, stopping adding acid, repeating the adding process of the concentrated sulfuric acid, finishing the acid washing operation of the cadmium dross when the pH value of ore pulp is stabilized between 4.5 and 5.0 for 30min, wherein the end-point pH value of the ore pulp is 4.5, and the whole acid washing process lasts for 1.0 h; the purpose of this process is to make the soluble matters such as zinc, sodium and cadmium oxide in cadmium dross enter the solution as much as possible.
(2) And (3) physically separating the ore pulp dissolved in the water washing in the step (1) to obtain liquid ore pulp and blocky objects. The liquid ore pulp is subjected to subsequent reaction, and the block-shaped material returns to the cadmium mass smelting furnace to produce crude cadmium, and the process aims to directly and comprehensively recover all large-particle metals.
(3) Controlling the temperature of the ore pulp in the step (2) at 85 ℃, simultaneously slowly adding manganese dioxide and concentrated sulfuric acid for oxidation leaching, stopping adding concentrated sulfuric acid when the pH value of the solution is less than or equal to 1.5, continuing the reaction, replenishing oxidant manganese dioxide and concentrated sulfuric acid until the pH value is 1.5 when the pH value of the solution is higher than 3.0, stopping adding acid, repeating the adding process of the concentrated sulfuric acid, finishing the acid washing operation of cadmium scum when the pH value of the ore pulp is stabilized between 1.5 and 3.0 for 30min, wherein the end-point pH value of the ore pulp is 2.5, and the whole acid washing process lasts for 3.0 h; in the reaction process, oxidants including manganese dioxide and concentrated sulfuric acid are both consumables, so that in the experimental process, the conditions of the color and the pH value of the liquid need to be continuously detected and supplemented in time to ensure that the reaction is fully carried out.
(4) And (3) filtering the leachate obtained in the step (3), continuously leaching the filter residue in a copper-cadmium residue leaching process, and recovering zinc and cadmium from the filtrate in a cadmium preparation process.
The liquid comprises the following main components: zn: 50.78g/l, Cd: 56.23g/l, Mn: 18.76g/l, acidity 10.75g/l, slag component Zn: 2.01%, Cd: 4.52 percent.
Example 3
In the method for comprehensively recycling zinc and cadmium from cadmium dross, the cadmium dross comprises the following main components in percentage by weight: zn: 29.21%, Cd: 36.12 percent.
(1) Taking 410 g of cadmium dross, adding water into the cadmium dross according to a liquid-solid volume ratio of 5:1, heating the cadmium dross to 70 ℃ of water, simultaneously slowly adding concentrated sulfuric acid, stopping adding concentrated sulfuric acid when the pH value of the solution is less than or equal to 4.5, continuing the reaction, supplementing the concentrated sulfuric acid until the pH value is 4.5 when the pH value of the solution is higher than 5.0, stopping adding acid, repeating the adding process of the concentrated sulfuric acid, finishing the acid washing operation of the cadmium dross when the pH value of ore pulp is stabilized between 4.5 and 5.0 for 30min, wherein the end-point pH value of the ore pulp is 4.5, and the whole acid washing process lasts for 1.0 h; the purpose of this process is to make the soluble matters such as zinc, sodium and cadmium oxide in cadmium dross go into solution as much as possible.
(2) And (3) physically separating the ore pulp dissolved in the water washing in the step (1) to obtain liquid ore pulp and blocky objects. The liquid ore pulp is subjected to subsequent reaction, and the block-shaped material returns to the cadmium mass smelting furnace to produce the crude cadmium, so that the process aims to reflect the liquid environment for subsequent obtaining and simultaneously directly and comprehensively recover all large-particle metals.
(3) Controlling the water temperature in the ore pulp in the step (2) to 80 ℃, simultaneously slowly adding manganese dioxide and concentrated sulfuric acid for oxidation leaching, stopping adding concentrated sulfuric acid when the pH value of the solution is less than or equal to 1.5, continuing the reaction, supplementing oxidants of manganese dioxide and concentrated sulfuric acid until the pH value is 1.5 when the pH value of the solution is higher than 3.0, stopping adding acid, repeating the adding process of concentrated sulfuric acid, finishing the acid washing operation of cadmium dross when the pH value of the ore pulp is stabilized between 1.5 and 3.0 for 30min, wherein the end-point pH value of the ore pulp is 2.5, and the whole acid washing process lasts for 3.0 h; in the reaction process, oxidants including manganese dioxide and concentrated sulfuric acid are both consumables, so that in the experimental process, the conditions of the color and the pH value of the liquid need to be continuously detected and supplemented in time to ensure that the reaction is fully carried out.
(4) And (3) filtering the leachate obtained in the step (3), continuously leaching the filter residue in a copper-cadmium residue leaching process, and recovering zinc and cadmium from the filtrate in a cadmium preparation process.
The liquid comprises the following main components: zn: 59.01g/l, Cd: 75.91g/l, Mn: 24.80g/l, acidity 35.43g/l, slag component Zn: 0.42%, Cd: 4.56 percent.
The liquid comprises the following main components: zn: 50.78g/l, Cd: 56.23g/l, Mn: 18.76g/l, acidity 10.75g/l, slag component Zn: 2.01%, Cd: 4.52 percent.
The technical solutions provided by the embodiments of the present invention are described in detail above, and the principles and implementations of the embodiments of the present invention are explained herein by using specific examples, and the descriptions of the above embodiments are only used to help understand the principles of the embodiments of the present invention, and meanwhile, for a person of ordinary skill in the art, according to the embodiments of the present invention, there may be changes in the specific implementations and the application ranges, and in summary, the contents of the present description should not be understood as limiting the present invention.
Claims (5)
1. A method for comprehensively recycling zinc and cadmium from cadmium dross is characterized by comprising the following steps:
step one, acid pickling of cadmium dross: adding cadmium dross produced by a cadmium mass smelting furnace into hot water, wherein the volume ratio of the cadmium dross to the hot water is 1:4-5, adding a small amount of concentrated sulfuric acid into the hot water, fully reacting and dissolving the concentrated sulfuric acid and the cadmium dross, and continuously stirring to fully dissolve the concentrated sulfuric acid and the cadmium dross to form ore pulp;
step two, solid-liquid separation: adding clear water into the ore pulp for water washing, filtering the water-washed ore pulp to obtain liquid ore pulp and a block, and returning the block to the cadmium mass smelting furnace to produce crude cadmium;
step three, cadmium scum leaching: adding manganese dioxide into the liquid ore pulp for oxidation, simultaneously adding concentrated sulfuric acid for leaching, controlling reaction conditions, continuously detecting the color and the pH value of the liquid ore pulp, supplementing the manganese dioxide and the concentrated sulfuric acid in time to ensure that the reaction is fully carried out, and reacting the manganese dioxide with zinc and cadmium in the ore pulp to obtain leachate containing zinc and cadmium in ionic forms;
step four, filtering and recycling: and filtering the leaching solution to obtain filter residue and filtrate, returning the filter residue to the third copper-cadmium residue leaching procedure for continuous leaching, and returning the filtrate to the cadmium preparation procedure to recover zinc and cadmium.
2. The method for comprehensively recycling zinc and cadmium by using cadmium dross according to claim 1, wherein the method comprises the following steps: the temperature of the hot water in the first step is 60-80 ℃, the reaction time of washing the ore pulp in the first step is 0.5-1h, and the pH value is 4.5-5.0.
3. The method for comprehensively recycling zinc and cadmium by using cadmium dross according to claim 1, wherein the method comprises the following steps: in the second step, the volume ratio of the ore pulp to the clear water is 1: 4-5.
4. The method for comprehensively recycling zinc and cadmium by using cadmium dross according to claim 1, wherein the method comprises the following steps: and in the third step, the reaction conditions comprise the temperature of the liquid ore pulp, the leaching time and the pH value.
5. The method for comprehensively recycling zinc and cadmium by using cadmium dross according to claim 4, wherein the method comprises the following steps: the temperature is 80-90 ℃, the leaching time is 3-4h, and the pH value is 1.5-3.0.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202210447971.5A CN114717421A (en) | 2022-04-20 | 2022-04-20 | Method for comprehensively recycling zinc and cadmium from cadmium scum |
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| CN202210447971.5A CN114717421A (en) | 2022-04-20 | 2022-04-20 | Method for comprehensively recycling zinc and cadmium from cadmium scum |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101255502A (en) * | 2008-04-02 | 2008-09-03 | 河南豫光金铅股份有限公司 | Process for comprehensive recovery of indium, cadmium, thallium and zinc from lead system smoke |
| CN110699547A (en) * | 2019-08-23 | 2020-01-17 | 白银有色集团股份有限公司 | Method for recovering zinc and cadmium from waste alkaline residues |
| WO2021147803A1 (en) * | 2020-01-20 | 2021-07-29 | 昆明瀚创科技有限公司 | Device and control method for removing nickel, cobalt and germanium in zinc sulfate solution by means of continuous deep purification |
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- 2022-04-20 CN CN202210447971.5A patent/CN114717421A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101255502A (en) * | 2008-04-02 | 2008-09-03 | 河南豫光金铅股份有限公司 | Process for comprehensive recovery of indium, cadmium, thallium and zinc from lead system smoke |
| CN110699547A (en) * | 2019-08-23 | 2020-01-17 | 白银有色集团股份有限公司 | Method for recovering zinc and cadmium from waste alkaline residues |
| WO2021147803A1 (en) * | 2020-01-20 | 2021-07-29 | 昆明瀚创科技有限公司 | Device and control method for removing nickel, cobalt and germanium in zinc sulfate solution by means of continuous deep purification |
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