CN115636490A - Dechlorination method for chlorine-containing rare earth wastewater - Google Patents
Dechlorination method for chlorine-containing rare earth wastewater Download PDFInfo
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- CN115636490A CN115636490A CN202211506505.6A CN202211506505A CN115636490A CN 115636490 A CN115636490 A CN 115636490A CN 202211506505 A CN202211506505 A CN 202211506505A CN 115636490 A CN115636490 A CN 115636490A
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- rare earth
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- 239000002351 wastewater Substances 0.000 title claims abstract description 39
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 34
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 34
- 238000000034 method Methods 0.000 title claims abstract description 32
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 239000000460 chlorine Substances 0.000 title claims abstract description 26
- 229910052801 chlorine Inorganic materials 0.000 title claims abstract description 26
- 238000006298 dechlorination reaction Methods 0.000 title claims abstract description 25
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000011889 copper foil Substances 0.000 claims abstract description 42
- 238000006243 chemical reaction Methods 0.000 claims abstract description 38
- 239000007788 liquid Substances 0.000 claims abstract description 26
- 229940116318 copper carbonate Drugs 0.000 claims abstract description 24
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 claims abstract description 24
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000000926 separation method Methods 0.000 claims abstract description 16
- 239000002699 waste material Substances 0.000 claims abstract description 16
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims abstract description 13
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims abstract description 13
- 229940045803 cuprous chloride Drugs 0.000 claims abstract description 12
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 9
- 239000007787 solid Substances 0.000 claims abstract description 9
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 8
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 31
- 238000003756 stirring Methods 0.000 claims description 16
- 239000000843 powder Substances 0.000 claims description 10
- 238000004064 recycling Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 4
- 230000018044 dehydration Effects 0.000 claims description 2
- 238000006297 dehydration reaction Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000012216 screening Methods 0.000 claims description 2
- 230000000382 dechlorinating effect Effects 0.000 claims 6
- 238000007873 sieving Methods 0.000 abstract description 7
- 230000008901 benefit Effects 0.000 abstract description 3
- 239000000203 mixture Substances 0.000 abstract description 3
- 238000007599 discharging Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 21
- 238000003723 Smelting Methods 0.000 description 9
- 238000001514 detection method Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 239000012716 precipitator Substances 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 description 1
- 239000005750 Copper hydroxide Substances 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 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
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- XFWJKVMFIVXPKK-UHFFFAOYSA-N calcium;oxido(oxo)alumane Chemical compound [Ca+2].[O-][Al]=O.[O-][Al]=O XFWJKVMFIVXPKK-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229910001956 copper hydroxide Inorganic materials 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
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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
-
- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
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- Removal Of Specific Substances (AREA)
Abstract
The invention discloses a dechlorination method of chlorine-containing rare earth wastewater, which comprises the steps of adding basic copper carbonate and waste copper foil in waste lithium ion batteries to react with the chlorine-containing rare earth wastewater, preparing a carbon dioxide gas product in the reaction process, carrying out solid-liquid separation on the reacted mixture, discharging the obtained liquid which is dechlorinated solution directly, sieving the obtained solid, returning the oversize product which is the residual copper foil in the reaction, and selling the undersize product which is cuprous chloride directly. The method has the advantages of good dechlorination effect, low cost, no secondary pollution and high economic benefit.
Description
Technical Field
The invention belongs to the technical field of wastewater treatment, and relates to a method for removing chloride ions in rare earth smelting wastewater.
Background
With the increasing shortage of water resources and the trend of people to green and healthy life, the country advocates the recycling of the water resources vigorously and reduces the pollutants from entering the water body. Hydrochloric acid is generally adopted as a leaching agent of rare earth ore in the rare earth smelting industry, so that a large amount of chloride ions are remained in rare earth wastewater, and the direct discharge of the wastewater can destroy the ecological balance of water, pollute the environment and endanger the health and safety of people.
The existing methods for removing chloride ions in wastewater comprise evaporation, precipitation, membrane separation and the like, and can achieve higher chlorine removal rate, but the chlorine removal cost is higher, and some methods can also bring secondary pollution. For example, CN 112758958A discloses a method for removing chloride ions from a sodium sulfate solution, which comprises adding sulfuric acid into the chlorine-containing solution to adjust the pH value to 1.5 to 3.5, adding copper hydroxide and a reducing gas sulfur dioxide for reaction to generate CuCl precipitate so as to remove the chloride ions. For another example, the method for removing chloride ions in desulfurization wastewater disclosed as CN 113683249A proposes adding calcium aluminate to chlorine-containing wastewater for pretreatment, removing the primary precipitate after pretreatment, adding calcium hydroxide and aluminum powder, adjusting the pH to be alkaline, performing ultrasonic treatment, and then performing heating treatment to generate hydrated calcium chloroaluminate secondary precipitate, thereby removing chloride ions.
In recent years, the number of waste lithium ion batteries is increased sharply due to the wide application of the lithium ion batteries, and the dual pressure of resource shortage and environmental pollution can be relieved by recycling the waste lithium ion batteries, however, the valuable metals such as nickel, cobalt, manganese, lithium and the like in the anode material are mainly recycled in the lithium ion battery recycling industry at present, and little attention is paid to the recycling of the waste copper foil of the cathode.
Disclosure of Invention
The invention provides a dechlorination method for chlorine-containing rare earth wastewater, which has low cost, environmental protection and easy operation, can remove chloride ions in the rare earth wastewater, can also utilize copper foils in waste lithium ion batteries, and does not generate secondary pollution in the dechlorination process.
In order to achieve the aim, the invention provides a dechlorination method of chlorine-containing rare earth wastewater, which comprises the following steps:
(1) Adding basic copper carbonate into the chlorine-containing rare earth wastewater, adding the waste copper foil, and stirring until the reaction is complete;
(2) After the reaction is finished, carrying out solid-liquid separation on the obtained turbid liquid, wherein the obtained liquid is dechlorination waste water and can be directly discharged; and (2) screening the obtained solid, wherein oversize products are the residual copper foils after reaction, returning to the step (1) for reuse, and undersize products are cuprous chloride powder, and drying the cuprous chloride powder to serve as a product for sale.
In the method, in the step (1), the basic copper carbonate is added according to the molar ratio of the basic copper carbonate to the chloride ions of 1-4: 1.
In the step (1), adding waste copper foil according to the molar ratio of the copper foil to the basic copper carbonate of 2-8: 1.
In the step (1), the reaction temperature is 20-80 ℃, and the reaction time is 2-12 hours.
In the step (1), carbon dioxide gas generated in the reaction process can be collected and can be directly sold after dehydration and drying.
In the step (1), the waste copper foil can be waste copper foil generated in the lithium ion battery recycling process.
In the step (2), the used screen is a screen with the mesh number of 50-200 meshes.
Compared with the prior art, the technical scheme of the invention has the following beneficial effects:
(1) The method adopts the basic copper carbonate as the chloride ion precipitator, converts the basic copper carbonate into a cuprous chloride product with higher price, and the carbon dioxide released by the basic copper carbonate in the reaction process can be collected to be sold as a product, thereby not only realizing the removal of chloride ions, but also increasing the economic benefit of wastewater treatment.
(2) The method adopts the copper foil obtained in the recovery process of the waste lithium ion battery as the chloride ion precipitator, so that the copper foil waste is recovered and recycled, thereby not only being green and environment-friendly, but also reducing the cost of wastewater dechlorination.
Drawings
FIG. 1 is a flow chart of a dechlorination method of chlorine containing rare earth wastewater of example 1.
Detailed Description
The present invention will be further described with reference to the following examples and the accompanying drawings, but the present invention is not limited to the following examples.
Example 1
A dechlorination method of chlorine-containing rare earth wastewater is characterized by adding 1.5L of rare earth smelting wastewater with the chloride ion concentration of 15000mg/L into a 2L stirring reaction kettle, and then adding a solution of copper foil, basic copper carbonate and chloride ions according to the mol ratio of 4:1.1:1, adding copper foil and basic copper carbonate, stirring and reacting for about 12 hours at 20 ℃, and collecting gas generated in the reaction process to obtain a carbon dioxide gas product; carrying out solid-liquid separation on the turbid liquid obtained after the reaction to obtain a dechlorination solution, wherein the removal rate of chloride ions is 85% through detection; sieving the solid obtained by solid-liquid separation by using a sieve with 100 meshes, wherein oversize products are copper foils and returning the copper foils to the reaction kettle for use; the undersize product is cuprous chloride powder which can be directly sold after being dried. The flow of the dechlorination method is shown in figure 1.
Example 2
A dechlorination method of chlorine-containing rare earth wastewater is characterized by adding 0.8L of rare earth smelting wastewater with the chloride ion concentration of 10500mg/L into a 1L stirring reaction kettle, and then adding the rare earth smelting wastewater into the stirring reaction kettle according to the mol ratio of copper foil to basic copper carbonate to chloride ions of 8:2:1, adding copper foil and basic copper carbonate, stirring and reacting for about 4 hours at 70 ℃, and collecting gas generated in the reaction process to obtain a carbon dioxide gas product; carrying out solid-liquid separation on the turbid liquid obtained after the reaction to obtain a dechlorination solution, wherein the removal rate of chloride ions is 95% by detection; sieving the solid obtained by solid-liquid separation by using a sieve with 200 meshes, wherein oversize products are copper foils and returning the copper foils to the reaction kettle for use; the undersize product is cuprous chloride powder which can be directly sold after being dried.
Example 3
A dechlorination method of chlorine-containing rare earth wastewater is characterized by adding 9L of rare earth smelting wastewater with the chloride ion concentration of 20500mg/L into a 10L stirring reaction kettle, and then adding the mixture into the stirring reaction kettle according to the mol ratio of copper foil, basic copper carbonate and chloride ions of 6:2.5:1, adding copper foil and basic copper carbonate, stirring and reacting for about 9 hours at 50 ℃, and collecting gas generated in the reaction process to obtain a carbon dioxide gas product; carrying out solid-liquid separation on the turbid liquid obtained after the reaction to obtain a dechlorination solution, wherein the removal rate of chloride ions is 92% through detection; sieving the solid obtained by solid-liquid separation by using a sieve with the mesh number of 50 meshes, wherein oversize products are copper foils and returning the copper foils to the reaction kettle for use; the undersize product is cuprous chloride powder which can be directly sold after being dried.
Example 4
A dechlorination method of chlorine-containing rare earth wastewater is characterized by adding 18L of rare earth smelting wastewater with the chloride ion concentration of 18000mg/L into a 20L stirring reaction kettle, and then adding the mixture into a reactor according to the mol ratio of copper foil, basic copper carbonate and chloride ions of 7:3:1, adding copper foil and basic copper carbonate, stirring and reacting for about 10 hours at 40 ℃, and collecting gas generated in the reaction process to obtain a carbon dioxide gas product; carrying out solid-liquid separation on the turbid liquid obtained after the reaction to obtain a dechlorination solution, wherein the removal rate of chloride ions is 89% by detection; sieving the solid obtained by solid-liquid separation by using a sieve with the mesh number of 150 meshes, wherein oversize products are copper foils and returning the copper foils to the reaction kettle for use; the undersize product is cuprous chloride powder which can be directly sold after being dried.
Example 5
A dechlorination method of chlorine-containing rare earth wastewater is characterized by adding 4L of rare earth smelting wastewater with chloride ion concentration of 8000mg/L into a 5L stirring reaction kettle, and then adding a solution of copper foil, basic copper carbonate and chloride ions according to a mol ratio of 10:4:1, adding copper foil and basic copper carbonate, and stirring and reacting for about 7 hours at 60 ℃; carrying out solid-liquid separation on the turbid liquid obtained after the reaction to obtain a dechlorination solution, wherein the removal rate of chloride ions is 93% by detection; sieving the solid obtained by solid-liquid separation by using a sieve with the mesh number of 150 meshes, wherein oversize products are copper foils and returning the copper foils to the reaction kettle for use; the undersize product is cuprous chloride powder which can be directly sold after being dried.
Example 6
A dechlorination method of chlorine-containing rare earth wastewater is characterized by adding 9L of rare earth smelting wastewater with the chloride ion concentration of 6000mg/L into a 10L stirring reaction kettle, and then adding the raw materials according to the mol ratio of copper foil, basic copper carbonate and chloride ions of 5:1.5:1, adding copper foil and basic copper carbonate, and stirring and reacting at 20 ℃ for about 11 hours; carrying out solid-liquid separation on the turbid liquid obtained after the reaction to obtain a dechlorination solution, wherein the removal rate of chloride ions is 89% by detection; sieving the solid obtained by solid-liquid separation by using a sieve with the mesh number of 80 meshes, wherein oversize products are copper foils and returning the copper foils to the reaction kettle for use; the undersize product is cuprous chloride powder which can be directly sold after being dried.
Claims (7)
1. A dechlorination method for chlorine-containing rare earth wastewater is characterized by comprising the following steps:
(1) Adding basic copper carbonate into the chlorine-containing rare earth wastewater, adding the waste copper foil, and stirring until the reaction is finished;
(2) After the reaction is finished, carrying out solid-liquid separation on the obtained turbid liquid, wherein the obtained liquid is dechlorination wastewater and can be directly discharged; and (2) screening the obtained solid, wherein oversize products are the residual copper foils after reaction, returning to the step (1) for reuse, and undersize products are cuprous chloride powder, and drying the cuprous chloride powder to serve as a product for sale.
2. The method for dechlorinating chlorine-containing rare earth wastewater according to claim 1, which is characterized by comprising the following steps: in the step (1), basic copper carbonate is added according to the molar ratio of the basic copper carbonate to chloride ions of 1-4: 1.
3. The method for dechlorinating chlorine-containing rare earth wastewater according to claim 1, which is characterized by comprising the following steps: in the step (1), adding waste copper foil according to the molar ratio of the copper foil to the basic copper carbonate of 2-8: 1.
4. The method for dechlorinating chlorine-containing rare earth wastewater according to claim 1, which is characterized by comprising the following steps: in the step (1), the reaction temperature is 20-80 ℃ and the reaction time is 2-12 hours.
5. The method for dechlorinating chlorine-containing rare earth wastewater according to claim 1, which is characterized by comprising the following steps: in the step (1), the waste copper foil may be a waste copper foil generated in a lithium ion battery recycling process.
6. The method for dechlorinating chlorine-containing rare earth wastewater according to claim 1, which is characterized by comprising the following steps: in the step (1), carbon dioxide gas generated in the reaction process can be collected and can be directly sold after dehydration and drying.
7. The method for dechlorinating chlorine-containing rare earth wastewater according to claim 1, which is characterized by comprising the following steps: in the step (2), the used screen is a screen with the mesh number of 50-200 meshes.
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| CN202211506505.6A CN115636490A (en) | 2022-11-29 | 2022-11-29 | Dechlorination method for chlorine-containing rare earth wastewater |
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| CN106517621A (en) * | 2015-09-09 | 2017-03-22 | 有研稀土新材料股份有限公司 | Process of recycling wastewater containing ammonia chloride |
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| JP2020019664A (en) * | 2018-07-31 | 2020-02-06 | 住友金属鉱山株式会社 | Production method of high purity cobalt chloride aqueous solution |
| CN113060754A (en) * | 2021-03-16 | 2021-07-02 | 江苏理工学院 | Doped cuprous dechlorinating agent and preparation method and application thereof |
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2022
- 2022-11-29 CN CN202211506505.6A patent/CN115636490A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106517621A (en) * | 2015-09-09 | 2017-03-22 | 有研稀土新材料股份有限公司 | Process of recycling wastewater containing ammonia chloride |
| JP2020019664A (en) * | 2018-07-31 | 2020-02-06 | 住友金属鉱山株式会社 | Production method of high purity cobalt chloride aqueous solution |
| CN110255799A (en) * | 2019-06-11 | 2019-09-20 | 中国科学院生态环境研究中心 | A kind of dechlorination medicament and the methods and applications that are dechlorinated using it to acid water |
| CN113060754A (en) * | 2021-03-16 | 2021-07-02 | 江苏理工学院 | Doped cuprous dechlorinating agent and preparation method and application thereof |
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| Title |
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