CN111377416A - Method for recovering selenium from copper indium gallium selenium waste - Google Patents
Method for recovering selenium from copper indium gallium selenium waste Download PDFInfo
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- CN111377416A CN111377416A CN201811613524.2A CN201811613524A CN111377416A CN 111377416 A CN111377416 A CN 111377416A CN 201811613524 A CN201811613524 A CN 201811613524A CN 111377416 A CN111377416 A CN 111377416A
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- leaching
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- 239000011669 selenium Substances 0.000 title claims abstract description 79
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 title claims abstract description 76
- 229910052711 selenium Inorganic materials 0.000 title claims abstract description 76
- 238000000034 method Methods 0.000 title claims abstract description 55
- 239000002699 waste material Substances 0.000 title claims abstract description 30
- HVMJUDPAXRRVQO-UHFFFAOYSA-N copper indium Chemical compound [Cu].[In] HVMJUDPAXRRVQO-UHFFFAOYSA-N 0.000 title claims abstract description 15
- QNWMNMIVDYETIG-UHFFFAOYSA-N gallium(ii) selenide Chemical compound [Se]=[Ga] QNWMNMIVDYETIG-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 238000002386 leaching Methods 0.000 claims abstract description 104
- 239000000243 solution Substances 0.000 claims abstract description 49
- KTSFMFGEAAANTF-UHFFFAOYSA-N [Cu].[Se].[Se].[In] Chemical compound [Cu].[Se].[Se].[In] KTSFMFGEAAANTF-UHFFFAOYSA-N 0.000 claims abstract description 46
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims abstract description 43
- 239000000463 material Substances 0.000 claims abstract description 36
- 239000011259 mixed solution Substances 0.000 claims abstract description 25
- 230000020477 pH reduction Effects 0.000 claims abstract description 21
- 238000000926 separation method Methods 0.000 claims abstract description 16
- 239000003929 acidic solution Substances 0.000 claims abstract description 10
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 10
- 239000007788 liquid Substances 0.000 claims abstract description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 18
- 239000007787 solid Substances 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 150000007522 mineralic acids Chemical class 0.000 claims description 7
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 abstract description 9
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 238000001556 precipitation Methods 0.000 abstract description 8
- 238000005260 corrosion Methods 0.000 abstract description 7
- 230000007797 corrosion Effects 0.000 abstract description 7
- 238000000746 purification Methods 0.000 description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 9
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 9
- 229910052802 copper Inorganic materials 0.000 description 9
- 239000010949 copper Substances 0.000 description 9
- 229910052733 gallium Inorganic materials 0.000 description 9
- 229910052738 indium Inorganic materials 0.000 description 9
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 9
- 239000002253 acid Substances 0.000 description 8
- CJCPHQCRIACCIF-UHFFFAOYSA-L disodium;dioxido-oxo-selanylidene-$l^{6}-sulfane Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=[Se] CJCPHQCRIACCIF-UHFFFAOYSA-L 0.000 description 7
- 238000001914 filtration Methods 0.000 description 6
- 230000002378 acidificating effect Effects 0.000 description 5
- 239000002585 base Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000009841 combustion method Methods 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- JPJALAQPGMAKDF-UHFFFAOYSA-N selenium dioxide Chemical compound O=[Se]=O JPJALAQPGMAKDF-UHFFFAOYSA-N 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 238000005292 vacuum distillation Methods 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 3
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- 239000012670 alkaline solution Substances 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 238000010248 power generation Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 239000007832 Na2SO4 Substances 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 150000003346 selenoethers Chemical class 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B19/00—Selenium; Tellurium; Compounds thereof
- C01B19/02—Elemental selenium or tellurium
Abstract
The invention provides a method for recovering selenium from copper indium gallium selenium waste, which comprises the following steps: adding the copper indium gallium selenide material into a sulfite solution to obtain a mixed solution; leaching the mixed solution in a pressurized environment to obtain a leaching solution after leaching treatment; and adding an acidic solution into the leachate for acidification and decomposition, and then carrying out solid-liquid separation to obtain crude selenium. According to the method for recovering selenium from the CIGS waste, sulfite with mild property is used as a leaching agent, the CIGS material is leached under a pressurized environment, the requirement on corrosion resistance of equipment is low, the leaching time efficiency and the leaching rate of selenium can be ensured, and acid-base balance treatment is not needed subsequently; the selenium can be separated by two steps of leaching → acidification and precipitation, and the method has the advantages of short flow, high selenium separation efficiency and low production cost.
Description
Technical Field
The invention relates to the technical field of solid waste recovery, in particular to a method for recovering selenium from copper indium gallium selenium waste.
Background
The CIGS (copper indium gallium selenide) thin-film type solar power generation cell has the characteristics of being light, thin, easy to carry, high in energy conversion efficiency and the like, and is widely concerned. There are currently three main methods for its production: vacuum spraying, distillation, or non-vacuum spraying. By adopting any method, waste materials with high purity of copper, indium, gallium and selenium as main components are inevitably generated in the production process. The four metals have high values, and how to effectively separate and purify the four metals so as to be recycled as a CIGS battery production raw material or sold as pure metals has great economic and environmental significance.
One method for recovering selenium in copper indium gallium selenide in the prior art is an electrode electrolysis method; another method is acid or alkaline leaching followed by reduction to obtain crude selenium, e.g. leaching the waste powder in nitric acid to obtain a nitric acid leach solution, and adding a reducing agent to the nitric acid leach solution to obtain crude selenium by reduction. The former electrolysis method has a problem that the electrode result is difficult to control, and the latter method has high requirements on the whole corrosion resistance of equipment and high cost due to the fact that waste materials need to be leached by using an acidic or alkaline solution.
Disclosure of Invention
In order to solve the above problems, an object of the embodiments of the present invention is to provide a method for recovering selenium from copper indium gallium selenide waste.
The embodiment of the invention provides a method for recovering selenium from copper indium gallium selenium waste, which comprises the following steps:
adding the copper indium gallium selenide material into a sulfite solution to obtain a mixed solution;
leaching the mixed solution in a pressurized environment to obtain a leaching solution after leaching treatment;
and adding an acidic solution into the leachate for acidification and decomposition, and then carrying out solid-liquid separation to obtain crude selenium.
On the basis of the above embodiment, the pressurization environment is an environment with a pressure of 0.4 to 1.2 MPa.
On the basis of the above embodiment, the pressurization environment is an environment with a pressure of 0.7-0.9 MPa.
On the basis of the embodiment, the liquid-solid ratio of the sulfite solution to the CIGS material is (2-20): 1.
On the basis of the above examples, the amount of sulfite in the sulfite solution is 1 to 5 times the theoretical amount of selenium-completely-converted metal salt.
On the basis of the above embodiment, the leaching the mixed solution in a pressurized environment includes:
leaching the mixed solution in a pressurized environment for a preset time, wherein the leaching temperature is 30-270 ℃; the preset time is 0.5-8 hours.
On the basis of the embodiment, the leaching temperature is 150-210 ℃, and the preset time is 3-6 hours.
On the basis of the above embodiment, the adding an acidic solution into the leachate to perform an acidification and decomposition includes:
and adding inorganic acid into the leachate for acidification and decomposition, wherein the pH value of the acidification end point is less than 6.
On the basis of the above examples, the inorganic acids include: one or more of hydrochloric acid, sulfuric acid and nitric acid.
On the basis of the above embodiment, before the adding the material of copper indium gallium selenide into the sulfite solution, the method further includes:
and grinding the copper indium gallium selenide waste to obtain granular or powdery copper indium gallium selenide material.
In the scheme provided by the embodiment of the invention, sulfite with mild property is used as a leaching agent to leach the copper indium gallium selenide material in a pressurized environment, the leaching process is mild, the problem of equipment corrosion caused by acidic leaching or alkaline leaching is solved, the requirement on equipment corrosion resistance is low, and the leaching time efficiency and the selenium leaching rate can be ensured; and the sulfite has good selectivity to selenium, does not cause the synergistic leaching of copper, indium and gallium, and can realize effective separation in one step. Meanwhile, sulfite is used as a leaching agent, and acid-base balance treatment is not needed subsequently; the selenium can be separated by two steps of leaching → acidification and precipitation, and the method has the advantages of short flow, high selenium separation efficiency and low production cost.
In order to make the aforementioned and other objects, features and advantages of the present invention comprehensible, preferred embodiments accompanied with figures are described in detail below.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
Fig. 1 shows a flow chart of a method for recovering selenium from copper indium gallium selenide waste according to an embodiment of the invention;
fig. 2 shows a schematic flow of recovering selenium from copper indium gallium selenide waste provided by an embodiment of the invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The method for recovering selenium from copper indium gallium selenium waste provided by the embodiment of the invention is shown in figure 1 and comprises the following steps:
step 101: and adding the CIGS material into a sulfite solution to obtain a mixed solution.
In the embodiment of the invention, the copper indium gallium selenide material is a waste material which takes copper, indium, gallium and selenium with high purity as main components; the CIGS material can be specifically CIGS waste generated in the production of CIGS thin-film solar power generation cells, and can also be granular or powdery material obtained by grinding the CIGS waste. The method comprises the following steps of (1) crushing the copper indium gallium selenide waste by using a ball mill to obtain a granular copper indium gallium selenide material; meanwhile, the granularity of the copper indium gallium selenide material obtained after grinding is not larger than a preset threshold value. By grinding the copper indium gallium selenide waste, the copper indium gallium selenide waste can be conveniently and rapidly leached in the follow-up process, and the leaching efficiency is improved.
In the embodiment of the invention, the sulfite is specifically sodium sulfite (Na)2SO3) The concentration of the sulfite solution can be 50-300 g/L, and the liquid-solid ratio of the sulfite solution to the copper indium gallium selenide material is (2-20): 1. Specifically, the amount of sulfite in the sulfite solution needs to be more than the theoretical amount of selenium completely converted metal salt to ensure that the selenium is fully reflected; wherein the amount of sulfite in the sulfite solution is 1-5 times of the theoretical amount of selenium completely converted metal salt.
Step 102: and leaching the mixed solution in a pressurized environment to obtain a leaching solution after leaching treatment.
In the embodiment of the invention, the mixed solution refers to a liquid containing a sulfite solution and a copper indium gallium selenide material, namely, the copper indium gallium selenide material contains solid. And leaching the obtained mixed solution. In the embodiment of the invention, the mixed solution is leached under a pressurized environment so as to ensure the time efficiency and the leaching rate of selenium. Meanwhile, the sulfite is cheap and easy to obtain, and the sulfite is used as a leaching agent, so that the leaching process is mild, and the problem of equipment corrosion caused by acidic leaching or alkaline leaching is solved. Only selenium in the copper indium gallium selenium material reacts with sulfite, and the reaction during leaching of the mixed solution is as follows:
Na2SO3+Se＝Na2SeSO3；
and after leaching is finished, leaching solution containing selenium, namely sodium selenosulfate solution can be obtained, meanwhile, the copper indium gallium selenide material is changed into copper indium gallium residue, and then the copper indium gallium residue can be recycled by other modes, so that copper, indium and gallium in the copper indium gallium residue are recycled.
Specifically, the mixed solution may be subjected to leaching treatment in a pressure leaching tank. Those skilled in the art will understand that the mixed solution obtained in step 101 may be injected into a pressure leaching kettle for leaching, or the cigs material and the sulfite solution may be respectively injected into the pressure leaching kettle to obtain a mixed solution, and then leaching may be performed.
Optionally, in the embodiment of the present invention, the pressure environment during the leaching treatment is an environment with a pressure greater than a standard atmospheric pressure, and the pressure of the pressure environment may be specifically 0.4 to 1.2 MPa. Meanwhile, the leaching temperature in the leaching treatment is 30-270 ℃, and the preset leaching time is 0.5-8 hours. Preferably, the leaching temperature is 150-210 ℃, and the preset time is 3-6 hours. The leaching can reach higher temperature in a pressurizing environment, and metal selenides in the copper indium gallium selenide materials can be efficiently sheared in the pressurizing environment because the conventional sulfite can not shear the copper indium gallium selenide materials or the shearing rate is very low.
Step 103: adding an acidic solution into the leaching solution for acidification and decomposition, and then carrying out solid-liquid separation to obtain crude selenium.
In the embodiment of the invention, after the acidic solution and the leaching solution of the sodium selenosulfate are acidified and decomposed, solid crude selenium can be obtained. Wherein, the acid solution is specifically an inorganic acid solution, and the inorganic acid solution is: one or more of hydrochloric acid, sulfuric acid and nitric acid.
When the acidic solution is hydrochloric acid, the reaction process of the sodium selenosulfate leaching solution and the hydrochloric acid is as follows:
Na2SeSO3+2HCl＝2NaCl+Se↓+SO2↑+H2O；
namely, solid selenium can be generated after acidification and decomposition, and crude selenium can be obtained after solid-liquid separation. Simultaneously, SO obtained by the reaction2And the subsequent process can also be used for other purposes, so that the utilization rate of raw materials is improved.
When the acid solution is sulfuric acid, the reaction process of the sodium selenosulfate leaching solution and hydrochloric acid is as follows:
Na2SeSO3+H2SO4＝Na2SO4+Se↓+SO2↑+H2O；
optionally, inorganic acid is added into the leaching solution for acidification and decomposition, and the pH value at the acidification end is less than 6 so as to ensure the precipitation rate of selenium. And then, the crude selenium can be purified continuously, specifically, the crude selenium can be reduced by processes such as oxidation combustion method purification, selenium oxide purification and the like to obtain high-purity selenium, and impurities are further removed by deep purification and a vacuum distillation method to obtain the deep-purified high-purity metallic selenium. The recovery procedure in the embodiment of the present invention is schematically shown in fig. 2.
In the embodiment of the invention, the crude selenium can be obtained by the acid solution, and the selenium separation efficiency is high; compared with the traditional leaching reduction method, the traditional method needs to leach with an acidic or alkaline solution (for example, acid leaching is adopted, the concentration of residual acid is at least more than 10 g/L), and acid-base equilibrium treatment is needed subsequently; in the embodiment, sulfite is used as a leaching agent, so that acid-base balance treatment is not needed subsequently, and the efficiency is higher. In addition, in the embodiment, when the leachate is acidified, the acidification process only needs to be adjusted to slightly acidic (for example, pH 2), and even if the subsequent neutralization treatment is needed, the amount of alkali used is very small and can be ignored.
According to the method for recovering selenium from the copper indium gallium selenium waste, sulfite with mild property is used as a leaching agent, the copper indium gallium selenium material is leached under a pressurized environment, the leaching process is mild, the problem that equipment is corroded due to acid leaching or alkaline leaching does not exist, the requirement on corrosion resistance of the equipment is low, and the leaching time efficiency and the leaching rate of selenium can be ensured; and the sulfite has good selectivity to selenium, does not cause the synergistic leaching of copper, indium and gallium, and can realize effective separation in one step. Meanwhile, sulfite is used as a leaching agent, and acid-base balance treatment is not needed subsequently; the selenium can be separated by two steps of leaching → acidification and precipitation, and the method has the advantages of short flow, high selenium separation efficiency and low production cost.
The following describes the process of recovering selenium from copper indium gallium selenide waste materials by specific embodiments.
Example 1
The method for recovering selenium from the copper indium gallium selenium waste provided by the embodiment of the invention comprises the following steps:
step A1: adding 1kg of the CIGS material into 6L of 100g/L sulfite solution to obtain a mixed solution of the CIGS material and the sulfite solution.
Step A2: and putting the mixed solution into a pressure leaching kettle, closing the leaching kettle, keeping the pressure in the leaching kettle at 0.6MPa and the temperature at 180 ℃, and leaching for 5 hours.
Step A3: and filtering the copper indium gallium residues in the leaching kettle by using a solid-liquid separation device to obtain the leaching solution of the sodium selenosulfate.
And recovering the copper indium gallium residues by other modes after the copper indium gallium residues are obtained, and recovering copper, indium and gallium in the copper indium gallium residues.
Step A4: adding a proper amount of hydrochloric acid into the leaching solution until the pH value of the acidification end point is 2; filtering the solid crude selenium, wherein the precipitation rate of the selenium is not less than 99%.
Step A5: and purifying the crude selenium.
Specifically, the crude selenium can be reduced by processes such as oxidation combustion method purification, selenium oxide purification and the like to obtain high-purity selenium, and impurities are further removed by deep purification and vacuum distillation methods to prepare the deep-purified high-purity metallic selenium.
Example 2
The method for recovering selenium from the copper indium gallium selenium waste provided by the embodiment of the invention comprises the following steps:
step B1: and crushing the copper indium gallium selenide waste by using a ball mill to obtain a granular copper indium gallium selenide material.
Step B2: adding a proper amount of the CIGS material into 8L of 160g/L sulfite solution, wherein the liquid-solid ratio of the sulfite solution to the CIGS material is 15:1, and obtaining a mixed solution of the CIGS material and the sulfite solution.
Step B3: and putting the mixed solution into a pressure leaching kettle, closing the leaching kettle, keeping the pressure in the leaching kettle at 0.8MPa and the temperature at 170 ℃, and leaching for 4 hours.
Step B4: and filtering the copper indium gallium residues in the leaching kettle by using a solid-liquid separation device to obtain the leaching solution of the sodium selenosulfate.
And recovering the copper indium gallium residues by other modes after the copper indium gallium residues are obtained, and recovering copper, indium and gallium in the copper indium gallium residues.
Step B5: adding a proper amount of hydrochloric acid into the leaching solution until the pH value of the acidification end point is 0.21; filtering the solid crude selenium, wherein the precipitation rate of the selenium is not less than 99%.
Step B6: and purifying the crude selenium.
Specifically, the crude selenium can be reduced by processes such as oxidation combustion method purification, selenium oxide purification and the like to obtain high-purity selenium, and impurities are further removed by deep purification and vacuum distillation methods to prepare the deep-purified high-purity metallic selenium.
Example 3
The method for recovering selenium from the copper indium gallium selenium waste provided by the embodiment of the invention comprises the following steps:
step C1: and crushing the copper indium gallium selenide waste by using a ball mill to obtain 2kg of granular copper indium gallium selenide material.
Step C2: adding 2kg of the CIGS material into 10L of 150g/L sulfite solution to obtain a mixed solution of the CIGS material and the sulfite solution.
Step C3: and putting the mixed solution into a pressure leaching kettle, closing the leaching kettle, keeping the pressure of the leaching kettle at 1MPa and the temperature at 190 ℃, and leaching for 2 hours.
Step C4: and filtering the copper indium gallium residues in the leaching kettle by using a solid-liquid separation device to obtain the leaching solution of the sodium selenosulfate.
And recovering the copper indium gallium residues by other modes after the copper indium gallium residues are obtained, and recovering copper, indium and gallium in the copper indium gallium residues.
Step C5: adding a proper amount of hydrochloric acid into the leaching solution until the pH value of the acidification end point is 0.9; filtering the solid crude selenium, wherein the precipitation rate of the selenium is not less than 99%.
Step C6: and purifying the crude selenium.
Specifically, the crude selenium can be reduced by processes such as oxidation combustion method purification, selenium oxide purification and the like to obtain high-purity selenium, and impurities are further removed by deep purification and vacuum distillation methods to prepare the deep-purified high-purity metallic selenium.
According to the method for recovering selenium from the copper indium gallium selenium waste, sulfite with mild property is used as a leaching agent, the copper indium gallium selenium material is leached under a pressurized environment, the leaching process is mild, the problem that equipment is corroded due to acid leaching or alkaline leaching does not exist, the requirement on corrosion resistance of the equipment is low, and the leaching time efficiency and the leaching rate of selenium can be ensured; and the sulfite has good selectivity to selenium, does not cause the synergistic leaching of copper, indium and gallium, and can realize effective separation in one step. Meanwhile, sulfite is used as a leaching agent, and acid-base balance treatment is not needed subsequently; the selenium can be separated by two steps of leaching → acidification and precipitation, and the method has the advantages of short flow, high selenium separation efficiency and low production cost.
The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present invention, and all the changes or substitutions should be covered within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (10)
1. A method for recovering selenium from copper indium gallium selenium waste is characterized by comprising the following steps:
adding the copper indium gallium selenide material into a sulfite solution to obtain a mixed solution;
leaching the mixed solution in a pressurized environment to obtain a leaching solution after leaching treatment;
and adding an acidic solution into the leachate for acidification and decomposition, and then carrying out solid-liquid separation to obtain crude selenium.
2. The method according to claim 1, wherein the pressurized environment is an environment having a pressure of 0.4 to 1.2 MPa.
3. The method according to claim 1, wherein the pressurized environment is an environment having a pressure of 0.7 to 0.9 MPa.
4. The method according to claim 1, wherein the liquid-solid ratio of the sulfite solution to the CIGS material is (2-20): 1.
5. The method according to claim 1, wherein the amount of sulfite in the sulfite solution is 1 to 5 times the theoretical amount of selenium fully converted metal salt.
6. The method of claim 1, wherein the subjecting the mixed solution to a leaching process in a pressurized environment comprises:
leaching the mixed solution in a pressurized environment for a preset time, wherein the leaching temperature is 30-270 ℃; the preset time is 0.5-8 hours.
7. The method according to claim 6, wherein the leaching temperature is 150-210 ℃, and the preset time period is 3-6 hours.
8. The method according to claim 1, wherein the step of adding an acidic solution to the leachate for the acidification decomposition comprises:
and adding inorganic acid into the leachate for acidification and decomposition, wherein the pH value of the acidification end point is less than 6.
9. The method of claim 8, wherein the inorganic acid comprises: one or more of hydrochloric acid, sulfuric acid and nitric acid.
10. The method of any one of claims 1-9, further comprising, prior to the adding the CIGS material to the sulfite solution:
and grinding the copper indium gallium selenide waste to obtain granular or powdery copper indium gallium selenide material.
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