CN113698268B - Resource utilization method of R32 spent catalyst - Google Patents
Resource utilization method of R32 spent catalyst Download PDFInfo
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- CN113698268B CN113698268B CN202111121849.0A CN202111121849A CN113698268B CN 113698268 B CN113698268 B CN 113698268B CN 202111121849 A CN202111121849 A CN 202111121849A CN 113698268 B CN113698268 B CN 113698268B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
- C07C17/10—Preparation of halogenated hydrocarbons by replacement by halogens of hydrogen atoms
- C07C17/12—Preparation of halogenated hydrocarbons by replacement by halogens of hydrogen atoms in the ring of aromatic compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/08—Halides
- B01J27/10—Chlorides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/08—Halides
- B01J27/12—Fluorides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J38/00—Regeneration or reactivation of catalysts, in general
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
- B01J38/64—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using alkaline material; using salts
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G30/00—Compounds of antimony
- C01G30/006—Halides
- C01G30/007—Halides of binary type SbX3 or SbX5 with X representing a halogen, or mixed of the type SbX3X'2 with X,X' representing different halogens
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B39/00—Halogenation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
- C07C17/10—Preparation of halogenated hydrocarbons by replacement by halogens of hydrogen atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/62—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by introduction of halogen; by substitution of halogen atoms by other halogen atoms
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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
- 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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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a resource utilization method of an R32 dead catalyst, which comprises the following steps: (1) separation of R32 spent catalyst: extruding the R32 perforated material and separating solids from liquids by a filter; (2) reuse of the R32 waste liquid catalyst: adding the separated liquid in the step (1) into a mixture of hard alkali and a drying agent, stirring, carrying out solid-liquid separation, and adding the liquid into a reaction kettle for continuous reaction after the content of pentavalent antimony in the liquid is measured to prepare R32; (3) purification of R32 spent solid catalyst: introducing dichloromethane into the solid in the filter at a certain flow rate, washing until the effluent dichloromethane is colorless, taking out, drying and storing for later use; (4) use of R32 spent solid catalyst in nuclear chlorination: and (3) adding the dried catalyst solid in the step (3) into aromatic hydrocarbon, and introducing chlorine to react under stirring to obtain chlorinated aromatic hydrocarbon.
Description
Technical Field
The invention relates to the field of R32 catalysts, in particular to a resource utilization method of an R32 spent catalyst.
Background
The common catalyst for preparing R32 by liquid phase fluorination is antimony pentachloride, which is a stronger Lewis acid. In the reaction process, antimony fluoride can be generated with hydrogen fluoride to corrode the material of the reaction kettle, and once the welding part is not smooth enough or long-time gas-liquid scouring corrosion is carried out, carbon on the reaction kettle substrate can be exposed, so that a primary cell effect is formed, and corrosion perforation of the reaction kettle is aggravated.
After the reaction kettle is perforated, the raw materials are generally recycled, and the waste catalyst is only hydrolyzed and then subjected to harmless treatment. The treatment method not only can generate more solid waste, but also needs a large amount of precipitant, thereby generating a large amount of salt-containing wastewater. The catalyst is usually fluorinated during use, so that the catalyst component in the R32 reaction is not simply antimony pentachloride, but is a mixture of antimony fluorides, which typically undergo a valence change after a galvanic reaction to become trivalent antimony. Through sampling analysis of the catalyst in the reaction kettle, we find that after the reaction kettle is perforated, the pentavalent antimony component in the catalyst is greatly reduced, the trivalent antimony component is greatly increased, the trivalent antimony can reach about 80% generally, and most of the trivalent antimony also becomes antimony fluochloride, and the composition is SbCl 0.25 F 2.75 . The catalyst is insoluble in methylene chloride and is also difficult to activate, which is one of the reasons why the catalytic effect is getting worse with use. Therefore, the spent catalyst produced after the perforation of R32 is generally difficult to recycle.
In the nuclear chlorination of aromatic compounds, metal halides are generally used for chlorination, but among various metal halide catalysts, antimony trichloride is an excellent catalyst, has better selectivity and faster reaction rate, and is applied to nuclear chlorination. However, antimony trichloride has better solubility for chlorinated aromatic hydrocarbon, and the possibility that antimony pentachloride is generated by chlorination in the chlorination process is easy to occur, so that the catalyst is generally difficult to recycle, and the environmental problem of subsequent treatment is caused. The catalyst after R32 perforation is basically insoluble in chlorinated aromatic hydrocarbon and is more insoluble in general aromatic hydrocarbon compounds due to the low content of chlorine atoms, and is basically difficult to oxidize or chlorinate by chlorine, so that the catalyst is relatively easier to recycle and reuse.
According to the invention, the perforated R32 dead catalyst is separated and recovered, and is applied to the nuclear chlorination process of the aromatic compound, so that the dangerous solid dead catalyst can be recycled, and the problem that the common nuclear chlorination catalyst cannot be recycled after being dissolved in the raw material can be solved.
Disclosure of Invention
In order to solve the technical problems, the invention provides a recycling method of an R32 dead catalyst, which aims to separate and recycle R32 dangerous solid waste and is applied to the nuclear chlorination process of aromatic hydrocarbon, so that the problem that the existing aromatic hydrocarbon nuclear chlorination catalyst is difficult to recycle can be solved, and the environmental problem caused by perforation of an R32 reaction kettle can be reduced.
In order to achieve the technical purpose, the invention adopts the following technical scheme:
a resource utilization method of an R32 dead catalyst comprises the following preparation steps:
(1) Separation of R32 spent catalyst: extruding the R32 perforated material and separating solids from liquids by a filter;
(2) Recycling of the R32 waste liquid catalyst: adding the separated liquid in the step (1) into a mixture of hard alkali and a drying agent, stirring, carrying out solid-liquid separation, adding the liquid into a reaction kettle after measuring the content of pentavalent antimony, adding back the catalyst antimony pentachloride and dichloromethane according to a proportion, and continuing to react to prepare R32;
(3) Purification of R32 spent solid catalyst: introducing dichloromethane into the solid in the filter in the step (1) at a certain flow rate, washing until the dichloromethane flows out and is colorless, taking out the solid catalyst in the filter, drying in vacuum at 100 ℃ until the catalyst turns from black to grey-white, and storing the catalyst in a dryer for later use;
(4) Use of R32 spent solid catalyst in nuclear chlorination: and (3) adding the dried catalyst solid in the step (3) into aromatic hydrocarbon, and introducing chlorine to react under stirring to obtain chlorinated aromatic hydrocarbon, wherein the reaction chemical equation is shown below.
Preferably, the R32 spent catalyst comprises an R32 spent liquid catalyst R32 spent solid catalyst.
Further, the filter in step (1) may be a removable filter device.
Preferably, the R32 waste liquid catalyst is treated with a mixture of readily separable calcium oxide and calcium hydroxide.
Preferably, the aromatic hydrocarbon is halogenated benzene, halogenated toluene, nitrohalogenated benzene, amino halogenated benzene, hydroxyl halogenated benzene, sulfo halogenated benzene, alkyl halogenated benzene or other benzene ring substituent compounds. Preferably, the nuclear chlorination reaction is a liquid phase chlorination reaction, and may be classified into a solvent-free reaction and a solvent-borne reaction.
Preferably, in the nuclear chlorination reaction, the addition amount of the R32 waste solid catalyst is 0.1-2% of the mass of aromatic hydrocarbon.
Preferably, the nuclear chlorination reaction is a liquid phase chlorination reaction, and may be classified into a solvent-free reaction and a solvent-borne reaction.
Further, the nuclear chlorination reaction temperature does not exceed the boiling point of the starting materials and the solvent added.
Compared with the prior art, the invention has the following beneficial effects:
1. the method comprises the steps of carrying out solid-liquid separation on the R32 spent catalyst, carrying out solid-liquid treatment on the spent catalyst, carrying out treatment on the recycled liquid catalyst and raw materials, and returning the treated spent catalyst to an R32 reaction system; the recovered solid catalyst is treated to carry out nuclear chlorination catalytic reaction, and the invention realizes the resource utilization of the R32 spent catalyst.
2. The R32 waste liquid catalyst can be separated and reused, so that the raw materials can be recycled, the cost is saved, and the waste is reduced.
3. The R32 waste solid catalyst is used for nuclear chlorination reaction of aromatic hydrocarbon, so that the catalyst can be prevented from being dissolved in the aromatic hydrocarbon, and the problem that the common nuclear chlorination catalyst cannot be recycled after being dissolved in raw materials is solved.
Detailed Description
The invention will be further described with reference to specific examples
1. Preparation example
Separation of R32 spent catalyst
The reactant material after the R32 is perforated is extruded through a pipeline and passes through a detachable filter device to separate the solid catalyst from the liquid material in the reactant material. The liquid material was taken to a storage tank and the solids in the filter were then washed with dichloromethane until the outlet dichloromethane was colorless, and the washed dichloromethane was incorporated into the storage tank. Taking out the solid in the filter, placing in a vacuum drying oven, vacuum drying at 100 ℃ for 24 hours, changing the catalyst from black to grey-white, and storing in a dryer for standby.
50Kg of calcium oxide and 100Kg of calcium hydroxide are added into a reaction kettle provided with a condensing device in advance, then jacket cooling water is opened, materials in a storage tank are slowly pressed into the reaction kettle, and the temperature in the reaction kettle is kept below 40 ℃. Stirring for 3h, press-filtering, pressing the liquid into a storage tank, measuring the content of antimony (calculated by antimony pentachloride), adding back to a reaction kettle, supplementing back the catalyst antimony pentachloride and dichloromethane according to a proportion, and continuing to react to prepare R32.
Example 1
Preparation of Paralyl
Into a 2L reactor was added 1000g of toluene, 6g of R32 solid catalyst, and 1g of thiophenol, followed by stirring. Introducing chlorine at the speed of 0.2Kg/h at 50 ℃, controlling the reaction temperature to be 50-60 ℃, introducing chlorine for 4 hours, and stopping the reaction. Residual hydrogen chloride and chlorine in the reaction liquid are removed in vacuum at 60 ℃, the catalyst is separated and then rectified, and 244g of toluene, 710g of p-chlorotoluene, 390g of o-chlorotoluene and 17g of other impurities are obtained.
Example 2
Preparation of paradichlorobenzene
Into a 2L reaction flask, 1000g of chlorobenzene, 6g of R32 solid catalyst were added and stirred. Introducing chlorine at the speed of 0.2Kg/h at the temperature of 70 ℃ and controlling the reaction temperature to be 70-80 ℃, introducing chlorine for 4 hours, and stopping the reaction. Residual hydrogen chloride and chlorine in the reaction liquid are removed in vacuum at 80 ℃, and after the catalyst is separated and rectified, 1091g of p-dichlorobenzene, 158g of o-dichlorobenzene and m-dichlorobenzene and 18g of other impurities are obtained.
Example 3
Preparation of parachlorophenol
Into a 2L reactor was added 1000g of phenol, 6g of R32 solid catalyst, and 1g of thiophenol, followed by stirring. Introducing chlorine at the speed of 0.2Kg/h at 50 ℃, controlling the reaction temperature to be 50-60 ℃, introducing chlorine for 3h, and stopping the reaction. Residual hydrogen chloride and chlorine in the reaction liquid are removed in vacuum at 60 ℃, and after the catalyst is separated and rectified, 334g of phenol, 578g of p-chlorophenol, 310g of o-chlorophenol and 22g of other impurities are obtained.
Example 4
Preparation of 2, 4-dichlorotoluene:
into a 2L reaction flask, 1Kg of p-chlorotoluene and 6g of R32 solid catalyst were added and stirred. Introducing chlorine at the speed of 0.2Kg/h at normal temperature, controlling the reaction temperature to be 30-40 ℃, introducing chlorine for 2h, and stopping the reaction. Residual hydrogen chloride and chlorine in the reaction liquid are removed in vacuum at 40 ℃, and after the catalyst is separated and rectified, 210g of p-chlorotoluene, 696g of 2, 4-dichlorotoluene, 155g of 3, 4-dichlorotoluene and 106g of other impurities are obtained.
Example 5
Preparation of 3, 4-dichloro-benzotrifluoride
Into a 2L reactor was charged 1Kg of p-chlorotrifluorotoluene and 6g of R32 solid catalyst. Introducing chlorine at the speed of 0.2Kg/h at the temperature of 60 ℃ and controlling the reaction temperature to be 60-70 ℃, introducing chlorine for 1.5h, and stopping the reaction. Residual hydrogen chloride and chlorine in the reaction liquid are removed in vacuum at 70 ℃, and the catalyst is recovered after being separated and rectified to obtain 305g of p-chlorotrifluorotoluene, 768g of 3, 4-dichloro-benzotrifluoride and 17g of other impurities.
Example 6
1Kg of chlorotrifluorotoluene was charged into a 2L reactor, and the R32 solid catalyst was recovered. Introducing chlorine at the speed of 0.2Kg/h at the temperature of 60 ℃ and controlling the reaction temperature to be 60-70 ℃, introducing chlorine for 1.5h, and stopping the reaction. Residual hydrogen chloride and chlorine in the reaction liquid are removed in vacuum at 70 ℃, and after the catalyst is separated and rectified, 312g of p-chlorotrifluorotoluene, 759g of 3, 4-dichlorotrifluoro toluene and 17g of other impurities are obtained.
Through implementation of the embodiment, the waste solid catalyst after R32 recovery can be well applied to the nuclear chlorination process of aromatic hydrocarbon, is easy to recover and has good universality, and is a Lewis acid catalyst with higher selectivity. The method provides a new direction for the treatment of the waste catalyst, is beneficial to the resource utilization of similar solid catalysts, brings new economic benefits, and reduces the environmental impact and other problems caused by the treatment of waste.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and are not limiting; while the invention has been described in detail with reference to the above-described embodiments, those skilled in the art will appreciate that modifications may be made to the embodiments described in the foregoing description, or that certain features may be substituted for those illustrated in the drawings; such modifications and substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present invention.
Claims (7)
1. A resource utilization method of an R32 dead catalyst comprises the following preparation steps:
(1) Separation of R32 spent catalyst: extruding the R32 perforated material and separating solids from liquids by a filter;
(2) Recycling of the R32 waste liquid catalyst: adding the separated liquid in the step (1) into a mixture of hard alkali and a drying agent, stirring, carrying out solid-liquid separation, adding the liquid into a reaction kettle after measuring the content of pentavalent antimony, adding back the catalyst antimony pentachloride and dichloromethane according to a proportion, and continuing to react to prepare R32;
(3) Purification of R32 spent solid catalyst: introducing dichloromethane into the solid in the filter in the step (1) at a certain flow rate, washing until the dichloromethane flows out and is colorless, taking out the solid catalyst in the filter, drying in vacuum at 100 ℃ until the catalyst turns from black to grey-white, and storing the catalyst in a dryer for later use;
(4) Use of R32 spent solid catalyst in nuclear chlorination: adding the dried catalyst solid in the step (3) into aromatic hydrocarbon, stirring, and introducing chlorine to react to obtain chlorinated aromatic hydrocarbon, wherein the reaction chemical equation is shown as follows;
the R32 waste liquid catalyst is treated by a mixture of calcium oxide and calcium hydroxide which are easy to separate.
2. The method for recycling R32 spent catalyst according to claim 1, wherein the R32 spent catalyst comprises an R32 spent liquid catalyst and an R32 spent solid catalyst.
3. The method for recycling R32 spent catalyst according to claim 1, wherein the filter in step (1) is a detachable filter device.
4. The method for recycling R32 spent catalyst according to claim 1, wherein the aromatic hydrocarbon is halogenated benzene, halogenated toluene, nitrohalogenated benzene, aminohalogenated benzene, hydroxyhalogenated benzene, sulfohalogenated benzene, alkylhalogenated benzene.
5. The method for recycling R32 spent catalyst according to claim 4, wherein the nuclear chlorination is a liquid-phase chlorination, and the type of the nuclear chlorination is a solvent-free reaction type or a solvent-containing reaction type.
6. The recycling method of the R32 spent catalyst according to claim 5, wherein the addition amount of the R32 spent solid catalyst in the nuclear chlorination reaction is 0.1-2% of the mass of aromatic hydrocarbon.
7. The method for recycling R32 spent catalyst according to any one of claims 4 to 6, wherein the nuclear chlorination reaction temperature does not exceed the boiling points of the raw materials and the solvent added.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5620526A (en) * | 1979-07-31 | 1981-02-26 | Central Glass Co Ltd | Liquid-phase chlorofluorination |
| CN1042318A (en) * | 1988-10-26 | 1990-05-23 | 纳幕尔杜邦公司 | The processing method of spent antimony halide catelysts |
| CN103408163A (en) * | 2013-08-28 | 2013-11-27 | 山东东岳化工有限公司 | Treatment method of waste liquid in production of organic fluoride |
| CN103420784A (en) * | 2013-08-19 | 2013-12-04 | 江苏大学 | Toluene selective chlorination method |
| CN105601466A (en) * | 2015-11-18 | 2016-05-25 | 江苏联化科技有限公司 | Synthetic method of 2,3,6-trichlorotoluene |
| CN108458344A (en) * | 2018-06-28 | 2018-08-28 | 中化蓝天霍尼韦尔新材料有限公司 | A kind of pre-processing device and its processing method of Antimonous Oxide from Wasted Antimonic Chloride Catalyst |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB623227A (en) * | 1947-02-17 | 1949-05-13 | John William Croom Crawford | Improvements in or relating to the production of 3, 3, 3-trifluoro-1, 1, 2-trichloropropene-1 |
| US9567273B2 (en) * | 2012-12-13 | 2017-02-14 | Shell Oil Company | Process for preparing alkylate comprising an improved solids removal step |
-
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- 2021-09-24 CN CN202111121849.0A patent/CN113698268B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5620526A (en) * | 1979-07-31 | 1981-02-26 | Central Glass Co Ltd | Liquid-phase chlorofluorination |
| CN1042318A (en) * | 1988-10-26 | 1990-05-23 | 纳幕尔杜邦公司 | The processing method of spent antimony halide catelysts |
| CN103420784A (en) * | 2013-08-19 | 2013-12-04 | 江苏大学 | Toluene selective chlorination method |
| CN103408163A (en) * | 2013-08-28 | 2013-11-27 | 山东东岳化工有限公司 | Treatment method of waste liquid in production of organic fluoride |
| CN105601466A (en) * | 2015-11-18 | 2016-05-25 | 江苏联化科技有限公司 | Synthetic method of 2,3,6-trichlorotoluene |
| CN108458344A (en) * | 2018-06-28 | 2018-08-28 | 中化蓝天霍尼韦尔新材料有限公司 | A kind of pre-processing device and its processing method of Antimonous Oxide from Wasted Antimonic Chloride Catalyst |
Non-Patent Citations (2)
| Title |
|---|
| SbF5/PAF - a novel fluorinating reagent in preparing fluorine compounds;Quan, HD et al.;《Journal of Fluorine Chemistry》;第125卷(第7期);第1169-1172页 * |
| 利用氟代烃生产中的废锑催化剂制取三氯化锑;李景国等;《福建化工》;第24-26页 * |
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