CN113787082A - Harmless treatment method for waste catalyst generated in synthetic process of trichloropyridine sodium alcoholate - Google Patents
Harmless treatment method for waste catalyst generated in synthetic process of trichloropyridine sodium alcoholate Download PDFInfo
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- CN113787082A CN113787082A CN202111066229.1A CN202111066229A CN113787082A CN 113787082 A CN113787082 A CN 113787082A CN 202111066229 A CN202111066229 A CN 202111066229A CN 113787082 A CN113787082 A CN 113787082A
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- copper
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- waste catalyst
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- 238000000034 method Methods 0.000 title claims abstract description 44
- 239000003054 catalyst Substances 0.000 title claims abstract description 20
- 239000002699 waste material Substances 0.000 title claims abstract description 18
- WLARTYCFUUGKSW-UHFFFAOYSA-N ClC1=C(C(=NC=C1)Cl)Cl.[Na] Chemical compound ClC1=C(C(=NC=C1)Cl)Cl.[Na] WLARTYCFUUGKSW-UHFFFAOYSA-N 0.000 title claims abstract description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 38
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 claims abstract description 32
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052802 copper Inorganic materials 0.000 claims abstract description 24
- 239000010949 copper Substances 0.000 claims abstract description 24
- 239000007787 solid Substances 0.000 claims abstract description 23
- 239000005750 Copper hydroxide Substances 0.000 claims abstract description 19
- 229910001956 copper hydroxide Inorganic materials 0.000 claims abstract description 19
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 150000003839 salts Chemical class 0.000 claims abstract description 14
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 12
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 12
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000005751 Copper oxide Substances 0.000 claims abstract description 11
- 229910000431 copper oxide Inorganic materials 0.000 claims abstract description 11
- 239000003513 alkali Substances 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims abstract description 10
- 239000007788 liquid Substances 0.000 claims abstract description 9
- PVFOMCVHYWHZJE-UHFFFAOYSA-N trichloroacetyl chloride Chemical compound ClC(=O)C(Cl)(Cl)Cl PVFOMCVHYWHZJE-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims abstract description 6
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims abstract description 6
- 229940045803 cuprous chloride Drugs 0.000 claims abstract description 6
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims abstract description 5
- DVECBJCOGJRVPX-UHFFFAOYSA-N butyryl chloride Chemical compound CCCC(Cl)=O DVECBJCOGJRVPX-UHFFFAOYSA-N 0.000 claims abstract description 5
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims abstract description 5
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 5
- 238000007664 blowing Methods 0.000 claims abstract description 4
- 238000002485 combustion reaction Methods 0.000 claims abstract description 4
- 238000001914 filtration Methods 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims abstract description 4
- 239000002244 precipitate Substances 0.000 claims abstract description 4
- 239000011261 inert gas Substances 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 9
- 239000007789 gas Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 239000012065 filter cake Substances 0.000 claims description 4
- 238000004064 recycling Methods 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- 230000001988 toxicity Effects 0.000 claims description 4
- 231100000419 toxicity Toxicity 0.000 claims description 4
- 229910002090 carbon oxide Inorganic materials 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 239000002912 waste gas Substances 0.000 claims description 3
- UWICOIBBNNVXFV-UHFFFAOYSA-N sodium;3,4,5-trichloro-1h-pyridin-2-one Chemical compound [Na].ClC1=CNC(=O)C(Cl)=C1Cl UWICOIBBNNVXFV-UHFFFAOYSA-N 0.000 claims 4
- 229910000510 noble metal Inorganic materials 0.000 abstract description 3
- 230000001590 oxidative effect Effects 0.000 abstract 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000007259 addition reaction Methods 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229910001431 copper ion Inorganic materials 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- -1 sodium alkoxide Chemical class 0.000 description 2
- 239000002910 solid waste Substances 0.000 description 2
- XJFIKRXIJXAJGH-UHFFFAOYSA-N 5-chloro-1,3-dihydroimidazo[4,5-b]pyridin-2-one Chemical group ClC1=CC=C2NC(=O)NC2=N1 XJFIKRXIJXAJGH-UHFFFAOYSA-N 0.000 description 1
- 239000005945 Chlorpyrifos-methyl Substances 0.000 description 1
- 239000005627 Triclopyr Substances 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 238000005904 alkaline hydrolysis reaction Methods 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- SBPBAQFWLVIOKP-UHFFFAOYSA-N chlorpyrifos Chemical group CCOP(=S)(OCC)OC1=NC(Cl)=C(Cl)C=C1Cl SBPBAQFWLVIOKP-UHFFFAOYSA-N 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 230000002363 herbicidal effect Effects 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- DXEYVFFFVOFVOK-UHFFFAOYSA-N sodium;3,5,6-trichloro-1h-pyridin-2-one Chemical compound [Na].ClC=1C=C(Cl)C(=O)NC=1Cl DXEYVFFFVOFVOK-UHFFFAOYSA-N 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- REEQLXCGVXDJSQ-UHFFFAOYSA-N trichlopyr Chemical compound OC(=O)COC1=NC(Cl)=C(Cl)C=C1Cl REEQLXCGVXDJSQ-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B5/00—Operations not covered by a single other subclass or by a single other group in this subclass
-
- 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
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Catalysts (AREA)
- Processing Of Solid Wastes (AREA)
- Fire-Extinguishing Compositions (AREA)
Abstract
The invention discloses a harmless treatment method for a waste catalyst generated in the synthesis process of trichloropyridine sodium alcoholate, wherein the addition waste catalyst in the synthesis process of trichloropyridine sodium alcoholate is added with alkali liquor to adjust the PH, and added with active carbon; after the temperature of the feed liquid is raised for reaction, extracting a solvent and part of water, and recovering the solvent chlorobenzene; trichloroacetyl chloride, acrylonitrile and butyryl chloride are destroyed to generate corresponding salts; reacting copper chloride, cuprous chloride and alkali liquor to generate copper hydroxide and cuprous hydroxide, blowing air into the reaction kettle, oxidizing the cuprous hydroxide into copper hydroxide precipitate, and filtering out mixed solid of activated carbon and copper hydroxide; putting the mixed solid into an atmosphere furnace, drying and dehydrating the mixed solid, and reacting carbon in the mixed solid with copper oxide to obtain a mixture of crude copper, salt and a small amount of carbon; after the mixed solid is treated in the atmosphere furnace, the tail gas containing part of organic matters enters a secondary combustion chamber of the RTO incinerator for decomposition. The invention realizes harmless treatment and recovers and generates noble metals.
Description
Technical Field
The invention relates to a harmless treatment method for a waste catalyst generated in a trichloropyridine sodium alcoholate synthetic process.
Background
The 3,5, 6-trichloropyridin-2-ol sodium is an important intermediate for the synthesis of the insecticides chlorpyrifos-ethyl, chlorpyrifos-methyl and the herbicide triclopyr. The current economically feasible route for the industrial synthesis of sodium alkoxide is the trichloroacetyl chloride process.
The process of synthesizing sodium alkoxide by trichloro-acetyl chloride method is divided into four reaction steps: addition reaction, cyclization reaction, alkaline hydrolysis reaction, refining and purification. Wherein the addition reaction is the key to influence the yield, the production efficiency and the production cost.
Cuprous chloride is often used as a catalyst in the addition reaction process, the catalyst is filtered out after the synthesis is finished, and the waste catalyst contains: solvents such as chlorobenzene, copper chloride, cuprous chloride, trichloroacetyl chloride, acrylonitrile, butyryl chloride and the like have strong volatility, corrosiveness, irritation and toxicity, so the waste catalyst is used for management and control treatment of dangerous solid wastes.
Disclosure of Invention
The invention aims to provide a harmless treatment method for a waste catalyst generated in the synthetic process of trichloropyridine sodium alcoholate, which realizes harmless treatment and recovers generated precious metals.
The technical solution of the invention is as follows:
a harmless treatment method for a waste catalyst generated in a trichloropyridine sodium alcoholate synthetic process is characterized by comprising the following steps: comprises the following steps:
(1) adding an addition waste catalyst in the synthesis process of the trichloropyridine sodium alcoholate into alkali liquor to adjust the pH value, so that the reaction end point pH value is not less than 12, and adding active carbon;
(2) heating the feed liquid for reaction, azeotropically extracting a solvent and part of water, and recovering the solvent chlorobenzene by phase splitting; trichloroacetyl chloride, acrylonitrile and butyryl chloride are destroyed under the strong alkaline condition to generate corresponding salts, and toxicity and corrosivity are removed;
(3) reacting copper chloride, cuprous chloride and alkali liquor to generate copper hydroxide and cuprous hydroxide, then blowing air into the reaction kettle to oxidize the cuprous hydroxide into copper hydroxide precipitate, and filtering out mixed solid of active carbon and copper hydroxide;
(4) putting the mixed solid into an atmosphere furnace, drying and dehydrating the mixed solid under the protection of inert gas, and finally reacting carbon in the mixed solid with copper oxide to obtain a mixture of crude copper, salt and a small amount of carbon; stirring and washing with clear water, and removing the salt and a small amount of carbon to finally obtain red copper;
(5) and (4) treating the mixed solid in the atmosphere furnace in the step (4), and then feeding the tail gas containing part of organic matters into a secondary combustion chamber of the RTO incinerator for complete decomposition and harmless emission.
And (4) protecting the atmosphere furnace by using inert gas, heating the copper hydroxide filter cake to 200-400 ℃, then dehydrating, decomposing into copper oxide, and burning the copper oxide and active carbon at 800 ℃ to generate copper.
And (4) cooling to 30-80 ℃ under the protection of inert gas, adding water, stirring and washing, dissolving salt, stirring activated carbon in water to realize separation by utilizing the density difference between the activated carbon and copper, drying moisture of the moisture copper separated from solid and liquid under the reduced pressure drying condition of less than 80 ℃, and recovering the copper.
And water generated in the process flows to the previous working section for recycling.
The tail gas generated in the process of copper production by burning is connected to the RTO furnace, so that the waste gas is completely discharged up to the standard.
The invention has the advantages that:
(1) hazardous solid waste is subjected to harmless treatment, and the sustainable development of main products is increased.
(2) The chlorobenzene which is the raw material of the main product reaction is fully recycled again, so that the resource recycling is realized.
(3) The process recovery produces the red copper with high price, realizes the resource recovery and produces considerable economic benefit.
(4) The alkaline solution used in the process is sodium hydroxide but is not limited to, and can be aqueous solution such as potassium hydroxide and the like.
(5) Proper amount of alkali is added in the process, the PH value at the end point of the reaction is higher than 12, copper ions/cuprous ions in the system need to be fully precipitated, and the loss of noble metals is minimum.
(6) The addition of the activated carbon in the process can help to filter copper hydroxide/cuprous hydroxide (pure copper hydroxide/cuprous hydroxide is extremely difficult to carry out solid-liquid separation); on the other hand, the copper hydroxide is used as a reducing agent for subsequent copper hydroxide filter cake calcination and reacts with copper oxide to generate copper.
(7) After the solvent recovery is finished, air is blown in, and oxygen in the air reacts with cuprous hydroxide in the feed liquid under the condition of residual heat in the kettle to generate cupric hydroxide.
Drawings
The invention is further illustrated by the following figures and examples.
FIG. 1 is a schematic process flow diagram of one embodiment of the present invention.
Detailed Description
Example 1:
a harmless treatment method for a waste catalyst generated in a trichloropyridine sodium alcoholate synthetic process comprises the following steps:
(1) adding an addition waste catalyst in the synthesis process of the trichloropyridine sodium alcoholate into alkali liquor to adjust the pH value, so that the pH value of a reaction end point is not less than 12, fully precipitating copper ions/cuprous ions of a system, and minimizing loss of noble metals; and adding activated carbon; the alkali liquor is sodium hydroxide or potassium hydroxide aqueous solution.
(2) Heating the feed liquid for reaction, azeotropically extracting a solvent and part of water, and recovering the solvent chlorobenzene by phase splitting; trichloroacetyl chloride, acrylonitrile and butyryl chloride are destroyed under the strong alkaline condition to generate corresponding salts, and toxicity and corrosivity are removed;
(3) reacting copper chloride, cuprous chloride and alkali liquor to generate copper hydroxide and cuprous hydroxide, then blowing air into the reaction kettle to oxidize the cuprous hydroxide into copper hydroxide precipitate, and filtering out mixed solid of active carbon and copper hydroxide;
(4) putting the mixed solid into an atmosphere furnace, under the protection of inert gas (nitrogen or other inert gas), drying and dehydrating the mixed solid for decomposition, and finally reacting carbon in the mixed solid with copper oxide to obtain a mixture of crude copper, salt and a small amount of carbon; stirring and washing with clear water, and removing the salt and a small amount of carbon to finally obtain red copper;
specifically, the method comprises the following steps: and (4) protecting the atmosphere furnace by using inert gas, heating the copper hydroxide filter cake to 200-400 ℃, then dehydrating, decomposing into copper oxide, and burning the copper oxide and active carbon at 800 ℃ to generate copper.
And (4) cooling to 30-80 ℃ under the protection of inert gas, adding water, stirring and washing, dissolving salt, stirring activated carbon in water to realize separation by utilizing the density difference between the activated carbon and copper, drying moisture of the moisture copper separated from solid and liquid under the reduced pressure drying condition of less than 80 ℃, and recovering the copper.
(5) And (4) treating the mixed solid in the atmosphere furnace in the step (4), and then feeding the tail gas containing part of organic matters into a secondary combustion chamber of the RTO incinerator for complete decomposition and harmless emission.
The water produced in the process flows to the previous working section for recycling, and water saving is realized.
The tail gas generated in the process of copper production by burning is connected to the RTO furnace, so that the waste gas is completely discharged up to the standard, and no air pollution is caused.
Claims (5)
1. A harmless treatment method for a waste catalyst generated in a trichloropyridine sodium alcoholate synthetic process is characterized by comprising the following steps: comprises the following steps:
(1) adding an addition waste catalyst in the synthesis process of the trichloropyridine sodium alcoholate into alkali liquor to adjust the pH value, so that the reaction end point pH value is not less than 12, and adding active carbon;
(2) heating the feed liquid for reaction, azeotropically extracting a solvent and part of water, and recovering the solvent chlorobenzene by phase splitting; trichloroacetyl chloride, acrylonitrile and butyryl chloride are destroyed under the strong alkaline condition to generate corresponding salts, and toxicity and corrosivity are removed;
(3) reacting copper chloride, cuprous chloride and alkali liquor to generate copper hydroxide and cuprous hydroxide, then blowing air into the reaction kettle to oxidize the cuprous hydroxide into copper hydroxide precipitate, and filtering out mixed solid of active carbon and copper hydroxide;
(4) putting the mixed solid into an atmosphere furnace, drying and dehydrating the mixed solid under the protection of inert gas, and finally reacting carbon in the mixed solid with copper oxide to obtain a mixture of crude copper, salt and a small amount of carbon; stirring and washing with clear water, and removing the salt and a small amount of carbon to finally obtain red copper;
(5) and (4) treating the mixed solid in the atmosphere furnace in the step (4), and then feeding the tail gas containing part of organic matters into a secondary combustion chamber of the RTO incinerator for complete decomposition and harmless emission.
2. The method for harmlessly treating the waste catalyst generated in the synthesis process of the trichloropyridinol sodium as claimed in claim 1, which is characterized in that: and (4) protecting the atmosphere furnace by using inert gas, heating the copper hydroxide filter cake to 200-400 ℃, then dehydrating, decomposing into copper oxide, and burning the copper oxide and active carbon at 800 ℃ to generate copper.
3. The method for harmlessly treating the waste catalyst generated in the synthesis process of the trichloropyridinol sodium as claimed in claim 1, which is characterized in that: and (4) cooling to 30-80 ℃ under the protection of inert gas, adding water, stirring and washing, dissolving salt, stirring activated carbon in water to realize separation by utilizing the density difference between the activated carbon and copper, drying moisture of the moisture copper separated from solid and liquid under the reduced pressure drying condition of less than 80 ℃, and recovering the copper.
4. The method for harmlessly treating the waste catalyst generated in the synthesis process of the trichloropyridinol sodium as claimed in claim 1, which is characterized in that: and water generated in the process flows to the previous working section for recycling.
5. The method for harmlessly treating the waste catalyst generated in the synthesis process of the trichloropyridinol sodium as claimed in claim 2, which is characterized in that: the tail gas generated in the process of copper production by burning is connected to the RTO furnace, so that the waste gas is completely discharged up to the standard.
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| CN202111066229.1A CN113787082B (en) | 2021-09-13 | 2021-09-13 | Harmless treatment method for waste catalyst generated in synthetic process of trichloropyridine sodium alcoholate |
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| CN202111066229.1A CN113787082B (en) | 2021-09-13 | 2021-09-13 | Harmless treatment method for waste catalyst generated in synthetic process of trichloropyridine sodium alcoholate |
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05155819A (en) * | 1991-12-10 | 1993-06-22 | Daicel Chem Ind Ltd | Recovery of metal component from catalyst and production of alkali metal oxalate |
| CN1312391A (en) * | 2001-02-21 | 2001-09-12 | 谢祯辉 | Method of recovering metal from metal-containing sludge |
| US20010051103A1 (en) * | 2000-05-30 | 2001-12-13 | Seo Kyu Bum | Preparation of highly pure copper oxide from waste etchant |
| TW201113226A (en) * | 2009-10-13 | 2011-04-16 | Li Mei Electrical Entpr Co Ltd | Device and method for recovering copper metal from copper containing waste |
| CN102231435A (en) * | 2011-05-20 | 2011-11-02 | 合肥工业大学 | Method for preparing electrode material CuO (cupric oxide) film of lithium ion battery on copper substrate |
| CN106279005A (en) * | 2016-08-17 | 2017-01-04 | 重庆华歌生物化学有限公司 | A kind of method reclaiming trichloro pyridyl sodium alcoholate from trichloro pyridyl sodium alcoholate production waste material |
| US20210262659A1 (en) * | 2018-06-12 | 2021-08-26 | General Electric Company | System and method for processing an exhaust gas |
-
2021
- 2021-09-13 CN CN202111066229.1A patent/CN113787082B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05155819A (en) * | 1991-12-10 | 1993-06-22 | Daicel Chem Ind Ltd | Recovery of metal component from catalyst and production of alkali metal oxalate |
| US20010051103A1 (en) * | 2000-05-30 | 2001-12-13 | Seo Kyu Bum | Preparation of highly pure copper oxide from waste etchant |
| CN1312391A (en) * | 2001-02-21 | 2001-09-12 | 谢祯辉 | Method of recovering metal from metal-containing sludge |
| TW201113226A (en) * | 2009-10-13 | 2011-04-16 | Li Mei Electrical Entpr Co Ltd | Device and method for recovering copper metal from copper containing waste |
| CN102231435A (en) * | 2011-05-20 | 2011-11-02 | 合肥工业大学 | Method for preparing electrode material CuO (cupric oxide) film of lithium ion battery on copper substrate |
| CN106279005A (en) * | 2016-08-17 | 2017-01-04 | 重庆华歌生物化学有限公司 | A kind of method reclaiming trichloro pyridyl sodium alcoholate from trichloro pyridyl sodium alcoholate production waste material |
| US20210262659A1 (en) * | 2018-06-12 | 2021-08-26 | General Electric Company | System and method for processing an exhaust gas |
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