CN108842073B - Method for treating zinc-cadmium slag by alkaline process - Google Patents
Method for treating zinc-cadmium slag by alkaline process Download PDFInfo
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- 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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- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
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- C01F11/46—Sulfates
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- C22B19/00—Obtaining zinc or zinc oxide
- C22B19/20—Obtaining zinc otherwise than by distilling
- C22B19/24—Obtaining zinc otherwise than by distilling with leaching with alkaline solutions, e.g. ammonia
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Abstract
The invention provides a method for treating zinc-cadmium slag by an alkaline process, which comprises the following steps: (1) soaking the zinc-cadmium slag in NaOH solution, performing alkali dissolution reaction, and filtering to obtain sodium zincate solution and cadmium slag; (2) washing the cadmium slag with water to obtain waste cadmium slag and first washing water; (3) mixing the sodium zincate solution, the first washing water and slaked lime, performing precipitation reaction, and filtering to obtain waste alkali liquor and a crude calcium zincate product; (4) washing the crude calcium zincate product with water to obtain refined calcium zincate and second washing water; (5) mixing the waste alkali liquor with second washing water to prepare the NaOH solution in the step (1); (6) and mixing the refined calcium zincate with sulfuric acid, carrying out acidolysis reaction, and filtering to obtain a zinc sulfate solution and a calcium sulfate solid. The method for treating the zinc-cadmium slag by the alkaline method does not need to use zinc powder, can effectively recover the zinc, realizes zero discharge of waste liquid, and can produce calcium sulfate.
Description
Technical Field
The invention relates to the technical field of zinc-cadmium slag treatment, in particular to a method for treating zinc-cadmium slag by an alkaline method.
Background
A large amount of zinc-cadmium slag is generated in the purification and impurity removal process of the zinc hydrometallurgy process, wherein zinc exists in the form of ZnO and simple substances of Zn, cadmium exists in the form of CdO, simple substances of Cd and Cd (OH)2Exist in the form of (1). The traditional treatment method of zinc-cadmium slag is acid leaching method, i.e. the zinc-cadmium slag is dissolved by sulfuric acid, then the pH value of the solution is regulated to a certain acidity, zinc powder is added at proper temp. to replace cadmium in the solution, so that it becomes sponge cadmium to be separated out, then according to the purity of obtained sponge cadmium, it is determined whether to re-dissolve acid again, then zinc powder replacement is made, the obtained zinc sulfate solution is concentrated and combinedCrystallizing industrial zinc sulfate or sending to produce electrolytic zinc. The process is mature and stable and is easy to operate, but the zinc cadmium slag is high in treatment cost due to the fact that zinc powder needs to be used for replacement to remove cadmium after acid leaching.
Disclosure of Invention
The invention aims to provide a method for treating zinc-cadmium slag by an alkaline method, which does not need to add Zn powder to replace cadmium, thereby reducing the treatment cost of the zinc-cadmium slag.
In order to achieve the above object, the present invention provides the following technical solutions:
a method for treating zinc cadmium slag by an alkaline method comprises the following steps:
(1) soaking the zinc-cadmium slag in NaOH solution, performing alkali dissolution reaction, and filtering to obtain sodium zincate solution and cadmium slag;
(2) washing the cadmium slag with water to obtain waste cadmium slag and first washing water;
(3) mixing the sodium zincate solution, the first washing water and slaked lime, performing precipitation reaction, and filtering to obtain waste alkali liquor and a crude calcium zincate product;
(4) washing the crude calcium zincate product with water to obtain refined calcium zincate and second washing water;
(5) mixing the waste alkali liquor with second washing water to prepare the NaOH solution in the step (1);
(6) mixing the refined calcium zincate with sulfuric acid, carrying out acidolysis reaction, and filtering to obtain a zinc sulfate solution and a calcium sulfate solid;
the step (5) and the step (6) are not limited in time sequence.
Preferably, the concentration of the NaOH solution is 7-8 mol/L.
Preferably, the ratio of the mass (dry weight) of the zinc cadmium slag to the volume of the NaOH solution is 1g: 2.5-3.5 mL.
Preferably, the temperature of the alkali dissolution reaction is 55-65 ℃, and the time of the alkali dissolution reaction is 1.5-2.5 h.
Preferably, the molar ratio of the sodium zincate to the slaked lime is 1: 0.8-0.9 based on the sum of the amounts of the sodium zincate solution and the sodium zincate in the first washing water.
Preferably, the concentration of the sulfuric acid is 135-145 g/L.
Preferably, the ratio of the mass of the calcium zincate to the volume of the sulfuric acid is 1g: 8-12 mL.
Preferably, the acidolysis reaction time is 1-2 h.
Preferably, the ratio of the mass (dry weight) of the cadmium slag to the volume of the water in the step (2) is 1g: 3-3.5 mL.
Preferably, the ratio of the mass (dry weight) of the crude calcium zincate in the step (4) to the volume of water is 1g: 3-4 mL.
The invention provides a method for treating zinc-cadmium slag by an alkaline process, which comprises the following steps: (1) soaking the zinc-cadmium slag in NaOH solution, performing alkali dissolution reaction, and filtering to obtain sodium zincate solution and cadmium slag; (2) washing the cadmium slag with water to obtain waste cadmium slag and first washing water; (3) mixing the sodium zincate solution, the first washing water and slaked lime, performing precipitation reaction, and filtering to obtain waste alkali liquor and a crude calcium zincate product; (4) washing the crude calcium zincate product with water to obtain refined calcium zincate and second washing water; (5) mixing the waste alkali liquor with second washing water to prepare the NaOH solution in the step (1); (6) mixing the refined calcium zincate with sulfuric acid, carrying out acidolysis reaction, and filtering to obtain a zinc sulfate solution and a calcium sulfate solid; the step (5) and the step (6) are not limited in time sequence. The zinc-cadmium slag is immersed in the NaOH solution, zinc is converted into sodium zincate, and the sodium zincate is dissolved in the solution, so that the separation of zinc and cadmium is realized; mixing a sodium zincate solution with slaked lime to generate calcium zincate, and separating zinc; mixing the refined calcium zincate with sulfuric acid, and carrying out acidolysis reaction to generate calcium sulfate precipitate and zinc sulfate solution, wherein the calcium sulfate can be sold as a product, and the zinc sulfate solution can be returned to an electrolytic zinc workshop for zinc electrolysis or for producing zinc sulfate monohydrate; in addition, the waste alkali liquor and the washing water can be recycled for preparing the NaOH solution, so that zero emission of the waste liquor is realized. Therefore, the method for treating the zinc-cadmium slag by the alkaline method provided by the invention does not need to use expensive zinc powder, the zinc in the zinc-cadmium slag can be effectively recovered, the zero discharge of waste liquid is realized, and the calcium sulfate can be produced at the same time.
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FIG. 1 is a process flow diagram of the alkaline treatment of zinc cadmium slag.
Detailed Description
The invention provides a method for treating zinc-cadmium slag by an alkaline process, which comprises the following steps:
(1) soaking the zinc-cadmium slag in NaOH solution, performing alkali dissolution reaction, and filtering to obtain sodium zincate solution and cadmium slag;
(2) washing the cadmium slag with water to obtain waste cadmium slag and first washing water;
(3) mixing the sodium zincate solution, the first washing water and slaked lime, performing precipitation reaction, and filtering to obtain waste alkali liquor and a crude calcium zincate product;
(4) washing the crude calcium zincate product with water to obtain refined calcium zincate and second washing water;
(5) mixing the waste alkali liquor with second washing water to prepare the NaOH solution in the step (1);
(6) mixing the refined calcium zincate with sulfuric acid, carrying out acidolysis reaction, and filtering to obtain a zinc sulfate solution and a calcium sulfate solid;
the step (5) and the step (6) are not limited in time sequence.
The process flow diagram of the method for treating the zinc-cadmium slag by the alkaline method is shown in figure 1, the zinc-cadmium slag is immersed in NaOH solution, and after alkaline solution reaction, sodium zincate solution and cadmium slag are obtained by filtering; washing the cadmium slag with water, and dissolving a small amount of sodium zincate in the first washing water to obtain waste cadmium slag and first washing water; stacking waste cadmium slag; mixing the first washing water with a sodium zincate solution and slaked lime to generate a calcium zincate precipitate, and filtering to obtain a crude calcium zincate product and a waste alkali solution; washing the crude calcium zincate product with water, and dissolving sodium zincate in the crude calcium zincate product in second washing water to obtain refined calcium zincate and second washing water; a small amount of unreacted sodium zincate still exists in the waste alkali liquor, and the second washing water is mixed with the waste alkali liquor and can be used for preparing a leaching solution (namely a NaOH solution) for leaching zinc cadmium slag, so that the recycling of waste liquid is realized; the refined calcium zincate is mixed with sulfuric acid to generate calcium sulfate precipitate and zinc sulfate, wherein the zinc sulfate is dissolved in the solution and filtered to obtain zinc sulfate solution and calcium sulfate, the calcium sulfate can be sold as building materials, and the zinc sulfate solution can be directly returned to an electrolytic zinc workshop for electrolytic zinc and can also be used for producing zinc sulfate monohydrate.
The invention soaks the zinc-cadmium slag in NaOH solution, and after alkali dissolution reaction, the sodium zincate solution and the cadmium slag are obtained by filtering.
In the invention, the concentration of the NaOH solution is preferably 7-8 mol/L, and more preferably 7.5 mol/L.
In the present invention, the ratio of the mass (dry weight) of the zinc cadmium slag to the volume of the NaOH solution is preferably 1g:2.5 to 3.5mL, and more preferably 1g:2.8 to 3.2 mL.
In the invention, the temperature of the alkali dissolution reaction is preferably 55-65 ℃, and more preferably 60 ℃; the time of the alkali dissolution reaction is preferably 1.5-2.5 h, and more preferably 2.0 h; the time of the alkali-dissolution reaction is preferably from when the temperature required for the alkali-dissolution reaction is reached.
In the present invention, the alkali-soluble reaction is preferably kept in a stirred state during the alkali-soluble reaction; the stirring rotating speed is not particularly limited, and the conventional stirring rotating speed can be adopted.
In the invention, the product obtained by the alkali dissolution reaction can be cooled to room temperature and then filtered, or can be directly filtered without cooling; when the temperature is cooled to room temperature, the cooling rate is not particularly limited, and any cooling rate can be adopted; in an embodiment of the invention, the cooling is preferably natural cooling.
After the cadmium slag and the sodium zincate solution are obtained, the invention washes the cadmium slag with water to obtain waste cadmium slag and first washing water. In the invention, the cadmium slag is washed, and the sodium zincate in the cadmium slag can be dissolved in the washing water, so that the zinc and the cadmium are more fully separated.
The washing mode of the cadmium slag is not specially limited, and a conventional washing mode is adopted, in the embodiment of the invention, the washing mode is preferably to mix the cadmium slag and water, stir for 30min, and then filter to obtain waste cadmium slag and first washing water; according to the invention, a certain amount of water is preferably adopted to repeatedly wash cadmium slag, namely after one-time washing is finished, the obtained washing water is continuously used for the next-time washing; in the invention, the washing times of the cadmium slag are preferably 3-5 times; the ratio of the mass (dry weight) of the cadmium slag to the volume of water is preferably 1g: 3-3.5 mL.
After the cadmium slag is washed, the sodium zincate solution, the first washing water and the slaked lime are mixed, and after precipitation reaction and filtration, waste alkali liquor and a crude calcium zincate product are obtained.
In the present invention, the molar ratio of the sodium zincate to the slaked lime is preferably 1:0.8 to 0.9 in terms of the sum of the amounts of the sodium zincate solution and the sodium zincate in the first washing water. In the present invention, the amount of the substance of sodium zincate is preferably calculated by analyzing the content of zinc in the sodium zincate solution and the first washing water by polarography.
The source of the slaked lime is not particularly limited in the invention, and the slaked lime can be commercially available slaked lime or can be prepared from CaO and water. In the embodiment of the invention, CaO and water are mixed to prepare slaked lime preferably in an existing preparation mode; the existing preparation can reduce slaked lime and CO as much as possible2Reacting to ensure the activity of the used slaked lime.
The mixing sequence of the sodium zincate solution, the first washing water and the slaked lime is not particularly limited, and can be any mixing sequence.
In the present invention, the temperature of the precipitation reaction is preferably room temperature; the time of the precipitation reaction is preferably 1-2 h, and more preferably 1 h; the stirring state is preferably kept during the precipitation reaction; the stirring rotating speed is not particularly limited, and the conventional stirring rotating speed can be adopted.
After obtaining waste alkali liquor and a crude calcium zincate product, the invention washes the crude calcium zincate product with water to obtain refined calcium zincate and second washing water. In the invention, the crude calcium zincate is washed, so that the sodium zincate and the alkali in the crude calcium zincate can be fully washed out, and the calcium zincate with higher purity can be obtained.
In the embodiment of the invention, the washing mode is preferably to mix the crude calcium zincate with water, stir for 30min, and then filter to obtain refined calcium zincate and second washing water; according to the invention, a certain amount of water is preferably adopted to repeatedly wash the crude calcium zincate product, namely after one-time washing is finished, the obtained washing water is continuously used for the next-time washing; in the invention, the washing times of the crude calcium zincate product are preferably 3-5 times; the ratio of the mass (dry weight) of the calcium zincate crude product to the volume of water is preferably 1g: 3-4 mL.
After the crude calcium zincate product is washed, the waste alkali liquor and second washing water are mixed and then returned to the leaching (namely, alkali dissolution reaction) step of the zinc cadmium slag, and the waste alkali liquor is used for preparing a NaOH solution; and mixing the refined calcium zincate with sulfuric acid, carrying out acidolysis reaction, and filtering a product obtained by the acidolysis reaction to obtain a zinc sulfate solution and a calcium sulfate solid.
In the embodiment of the invention, the waste alkali solution is preferably mixed with the second washing water, evaporated and concentrated to the concentration of NaOH required for leaching the zinc cadmium slag (i.e. alkali dissolution reaction), and then directly used for leaching the zinc cadmium slag (i.e. alkali dissolution reaction).
In the invention, the concentration of the sulfuric acid is preferably 135-145 g/L, and more preferably 140 g/L.
In the present invention, the ratio of the mass (dry weight) of the calcium zincate to the volume of the sulfuric acid is preferably 1g:8 to 12mL, and more preferably 1g:10 mL.
In the invention, the acidolysis reaction time is preferably 1-2 h, and more preferably 1 h; the temperature of the acidolysis reaction is preferably room temperature; preferably, the acidolysis reaction is kept in a stirring state; the stirring rotating speed is not particularly limited, and the conventional stirring rotating speed can be adopted.
After the product obtained by the acidolysis reaction is filtered, the wet calcium sulfate product obtained by filtering is preferably dried to obtain calcium sulfate.
The drying mode is not particularly limited, and the calcium sulfate with constant weight can be obtained. In the present invention, the resulting calcium sulfate can be sold as a building material.
In the invention, after the product obtained by acidolysis reaction is filtered, the obtained zinc sulfate solution can be directly returned to an electrolytic zinc workshop for electrolytic zinc extraction; or can be prepared into zinc sulfate monohydrate by evaporation and concentration.
The following will explain the method for treating zinc cadmium slag by alkaline process provided by the present invention in detail with reference to the examples, but they should not be construed as limiting the scope of the present invention.
Example 1
(1) Mixing 1000g (dry weight) of zinc-cadmium slag with 3000mL of NaOH solution with the concentration of 7.5mol/L, heating to 60 ℃, carrying out alkali dissolution reaction for 2 hours, naturally cooling to room temperature, and filtering to obtain 2800mL of sodium zincate solution and 478g of cadmium slag; wherein the zinc cadmium slag contains 26.5 percent of Zn element by mass and 27.41 percent of Cd element by mass; testing the Zn content of the sodium zincate solution to be 91.8g/L by adopting a polarographic analysis method;
(2) mixing the cadmium slag with 1500mL of water, stirring for 30min, and then filtering to finish the first washing; repeating the washing process twice by using the filtrate obtained by filtering to obtain 476g of cadmium slag and 1420mL of first washing water; the content of Zn in the first washing water is tested to be 0.86g/L by adopting a polarographic analysis method, and the leaching rate of Zn is calculated to be 97.5%;
(3) calculating the total amount of sodium zincate in the sodium zincate solution and the first washing water, mixing the sodium zincate solution, the first washing water and slaked lime according to the ratio of the total amount of sodium zincate to the amount of slaked lime being 1:0.8, carrying out precipitation reaction at room temperature, after 1h of reaction, filtering the product obtained by the precipitation reaction to obtain 416.87g of crude calcium zincate and 4120mL of waste alkali liquor;
(4) mixing the crude calcium zincate with 1500mL of water, stirring for 30min, and then filtering to finish the first washing; repeating the washing process twice by using the filtrate obtained by filtering to obtain 409.67g of refined calcium zincate and 1340mL of second washing water;
(5) mixing second washing water with the waste alkali liquor, detecting the NaOH concentration of the obtained mixed liquor by adopting a hydrochloric acid titration method, and then evaporating and concentrating the obtained mixed liquor until the concentration of the obtained mixed liquor reaches 4-5 mol/L;
(6) mixing the refined calcium zincate with 4000mL of sulfuric acid with the concentration of 140g/L (the volume ratio of the dry weight of the calcium zincate to the sulfuric acid is 1g:10mL), carrying out acidolysis reaction at room temperature, reacting for 2h, and filtering to obtain 3750mL of zinc sulfate solution; the zinc content in the zinc sulfate solution obtained by polarographic analysis is 50.32g/L, and the recovery rate of zinc recovered from calcium zincate is calculated to be 97.08%.
(7) Evaporating and concentrating the zinc sulfate solution to obtain zinc sulfate monohydrate, and detecting by using an EDTA (ethylene diamine tetraacetic acid) complexation titration method to obtain the zinc content in the zinc sulfate monohydrate of 34.89%.
Example 2
(1) Mixing 1000g (dry weight) of zinc-cadmium slag with 3500ml of NaOH solution with the concentration of 7.5mol/L, heating to 60 ℃, reacting with an alkali solution for 2 hours, naturally cooling to room temperature, and filtering to obtain 3275ml of sodium zincate solution and 479g of cadmium slag; wherein the zinc cadmium slag contains 26.5 percent of Zn element by mass and 27.41 percent of Cd element by mass; testing the Zn content of the sodium zincate solution to be 78.65g/L by adopting a polarographic analysis method;
(2) mixing the cadmium slag with 1200ml of water, stirring for 30min, and then filtering to finish the first washing; repeating the above washing process twice using the filtrate obtained by the filtration to obtain 477.8g of cadmium slag and 1160ml of first washing water; the Zn content in the first washing water is tested to be 0.0097g/L by adopting a polarographic analysis method, and the calculated leaching rate of Zn is 98.3 percent;
(3) testing the zinc content in the sodium zincate solution and the first washing water by using a polarographic analysis method, calculating the total amount of substances of the sodium zincate in the sodium zincate solution and the first washing water, mixing the sodium zincate solution, the first washing water and the slaked lime according to the ratio of the total amount of the substances of the sodium zincate to the amount of the substances of the slaked lime of 1:0.9, carrying out precipitation reaction at room temperature for 1h, and filtering a product obtained by the precipitation reaction to obtain 473.95g of crude calcium zincate and 4325ml of waste alkali liquor;
(4) mixing the crude calcium zincate with 1450mL of water, stirring for 30min, then filtering to finish the first washing, and repeating the washing process twice by using filtrate obtained by filtering to obtain 471g of refined calcium zincate and 1300mL of second washing water;
(5) mixing second washing water with the waste alkali liquor, detecting by adopting a hydrochloric acid titration method to obtain NaOH concentration of the mixed liquor, and then evaporating and concentrating the obtained mixed liquor until the concentration of the obtained mixed liquor reaches 4-5 mol/L;
(6) mixing the refined calcium zincate with 4500mL of sulfuric acid with the concentration of 140g/L (the volume ratio of the dry weight of the calcium zincate to the sulfuric acid is 1g:10mL), carrying out acidolysis reaction at room temperature, reacting for 2h, filtering to obtain 4230mL of zinc sulfate solution, analyzing by polarography, wherein the content of zinc in the zinc sulfate solution is 51.45g/L, and the recovery rate of zinc recovered from the calcium zincate is 97.4% by calculation;
(7) evaporating the zinc sulfate solution to obtain zinc sulfate monohydrate, and detecting by using an EDTA (ethylene diamine tetraacetic acid) complexation titration method to obtain the zinc sulfate monohydrate with the content of 35%.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (8)
1. A method for treating zinc cadmium slag by an alkaline method comprises the following steps:
(1) soaking the zinc-cadmium slag in NaOH solution, performing alkali dissolution reaction, and filtering to obtain sodium zincate solution and cadmium slag; the concentration of the NaOH solution is 7-8 mol/L, and the ratio of the mass of the zinc cadmium slag to the volume of the NaOH solution is 1g: 2.5-3.5 mL;
(2) washing the cadmium slag with water to obtain waste cadmium slag and first washing water;
(3) mixing the sodium zincate solution, the first washing water and slaked lime, performing precipitation reaction, and filtering to obtain waste alkali liquor and a crude calcium zincate product;
(4) washing the crude calcium zincate product with water to obtain refined calcium zincate and second washing water;
(5) mixing the waste alkali liquor with second washing water to prepare the NaOH solution in the step (1);
(6) mixing the refined calcium zincate with sulfuric acid, carrying out acidolysis reaction, and filtering to obtain a zinc sulfate solution and a calcium sulfate solid;
the step (5) and the step (6) are not limited in time sequence;
the zinc-cadmium slag is produced in the purification and impurity removal process of the zinc hydrometallurgy process, zinc in the zinc-cadmium slag exists in the form of ZnO and a simple substance Zn, cadmium exists in the form of CdO, a simple substance Cd and Cd (OH)2Exist in the form of (1).
2. The method for treating the zinc-cadmium slag by the alkaline process according to claim 1, wherein the temperature of the alkaline dissolution reaction is 55-65 ℃, and the time of the alkaline dissolution reaction is 1.5-2.5 h.
3. The method for treating zinc-cadmium slag by using the alkaline process as claimed in claim 1, wherein the molar ratio of the sodium zincate to the slaked lime is 1: 0.8-0.9 based on the sum of the amounts of the sodium zincate solution and the sodium zincate in the first washing water.
4. The method for treating zinc-cadmium slag by using the alkaline process according to claim 1, wherein the concentration of the sulfuric acid is 135-145 g/L.
5. The method for treating zinc-cadmium slag by using the alkaline process as claimed in claim 4, wherein the ratio of the mass of the calcium zincate to the volume of the sulfuric acid is 1g: 8-12 mL.
6. The method for treating zinc-cadmium slag by using the alkaline process as claimed in claim 1, wherein the acidolysis reaction time is 1-2 h.
7. The method for treating zinc-cadmium slag by the alkaline process according to claim 1, wherein the ratio of the mass of the cadmium slag to the volume of water in the step (2) is 1g: 3-3.5 mL.
8. The method for treating zinc-cadmium slag by using the alkaline method as claimed in claim 1, wherein the ratio of the mass of the crude calcium zincate to the volume of water in the step (4) is 1g: 3-4 mL.
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| CN109455754B (en) * | 2019-01-02 | 2020-01-14 | 森克创能(天津)新能源科技有限公司 | Process and equipment for synthesizing calcium zincate as cathode material of zinc-nickel battery |
| 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 |
| CN113122735B (en) * | 2021-04-02 | 2022-11-15 | 云南云铜锌业股份有限公司 | Alkali-process zinc powder combined smelting method |
| CN115557719B (en) * | 2022-08-16 | 2023-08-15 | 湖北祥云(集团)化工股份有限公司 | Comprehensive treatment method of phosphogypsum |
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| CN1141956A (en) * | 1996-05-10 | 1997-02-05 | 北京有色冶金设计研究总院 | Method for production of zinc from material containing zinc |
| CN102505076A (en) * | 2011-06-01 | 2012-06-20 | 昆明同越科技开发有限公司 | Method for producing zinc powder and battery fluid from battery zinc anode waste and battery waste fluid |
| CN104232890A (en) * | 2013-06-14 | 2014-12-24 | 无锡市森信精密机械厂 | Wet metallurgy process for low-grade zinc oxide ores |
| CN105925810A (en) * | 2016-04-21 | 2016-09-07 | 西北矿冶研究院 | Method for preparing sponge cadmium from cadmium rectification alkaline residue |
| CN107460323A (en) * | 2017-08-11 | 2017-12-12 | 吴昊 | Cadmium alkaline residue harmless treatment process |
Non-Patent Citations (1)
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| 锌镉渣回收利用研究;邓洪民等;《世界有色金属》;20160425(第08期);第50页左栏第2段及图1、第51页表4 * |
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