WO2022121398A1 - Catalyseur d'hydrodéchloration et son application dans la préparation de chlorotrifluoroéthylène - Google Patents

Catalyseur d'hydrodéchloration et son application dans la préparation de chlorotrifluoroéthylène Download PDF

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WO2022121398A1
WO2022121398A1 PCT/CN2021/117090 CN2021117090W WO2022121398A1 WO 2022121398 A1 WO2022121398 A1 WO 2022121398A1 CN 2021117090 W CN2021117090 W CN 2021117090W WO 2022121398 A1 WO2022121398 A1 WO 2022121398A1
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catalyst
hydrodechlorination
activated carbon
carrier
preparation
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PCT/CN2021/117090
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English (en)
Chinese (zh)
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刘武灿
李玲
李小年
马超峰
石能富
卢春山
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中化蓝天集团有限公司
浙江蓝天环保高科技股份有限公司
浙江省化工研究院有限公司
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Priority claimed from CN202011454875.0A external-priority patent/CN112495394A/zh
Priority claimed from CN202011453854.7A external-priority patent/CN112547093B/zh
Application filed by 中化蓝天集团有限公司, 浙江蓝天环保高科技股份有限公司, 浙江省化工研究院有限公司 filed Critical 中化蓝天集团有限公司
Publication of WO2022121398A1 publication Critical patent/WO2022121398A1/fr

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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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/23—Preparation of halogenated hydrocarbons by dehalogenation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/35—Preparation of halogenated hydrocarbons by reactions not affecting the number of carbon or of halogen atoms in the reaction
    • C07C17/354—Preparation of halogenated hydrocarbons by reactions not affecting the number of carbon or of halogen atoms in the reaction by hydrogenation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C21/00—Acyclic unsaturated compounds containing halogen atoms
    • C07C21/02—Acyclic unsaturated compounds containing halogen atoms containing carbon-to-carbon double bonds
    • C07C21/18—Acyclic unsaturated compounds containing halogen atoms containing carbon-to-carbon double bonds containing fluorine

Definitions

  • the invention belongs to the field of chemical industry, and specifically relates to two hydrodechlorination catalysts, their preparation methods and their application in the preparation of chlorotrifluoroethylene.
  • Chlorotrifluoroethylene is a very important intermediate compound and polymerized monomer in industry. It is widely used in the preparation of various high value-added downstream products, including trifluoroethylene, hexafluorobutadiene, high-performance fluoropolymers, etc. .
  • the synthesis cost, purity and industrial feasibility of chlorotrifluoroethylene are the main factors affecting the development of chlorotrifluoroethylene and fluoropolymer materials. Therefore, it is of great significance to develop a high-purity, low-cost and environmentally friendly preparation process for chlorotrifluoroethylene.
  • Trifluorotrichloroethane (CFC-113) zinc powder reductive dechlorination method This method generally has large production equipment, low efficiency, and difficult to control production rate. In the reaction process, it needs to use a large amount of alcohol substances and zinc powder that are difficult to recover.
  • the by-products include trifluoroethylene, difluoroethylene, difluorochloroethylene, etc. Difficult to recycle, high cost of pollution treatment, etc.
  • Trifluorotrichloroethane catalytic hydrodechlorination method This method has the advantages of continuous production, no zinc chloride residue and no solvent, and has become the main industrial synthesis method.
  • Hydrodechlorination catalysts are the technical core of the hydrodechlorination process, mainly including Ni-based, supported precious metals, metal carbides and other heterogeneous catalysts and homogeneous catalysts. Supported noble metal catalysts are a hotspot in research and application due to their high activity and easy recovery.
  • CN1460549A discloses the catalyst used for preparing chlorotrifluoroethylene and trifluoroethylene by catalytic hydrodechlorination of 1,1,2-trifluoro-2,2,1-trichloroethane (CFC-113).
  • CFC-113 1,1,2-trifluoro-2,2,1-trichloroethane
  • Precious metal palladium and metal copper are the main active components, alkali metal lithium and rare earth metal (or metal lanthanum) are added as modification aids, and coconut shell activated carbon (referred to as coconut shell carbon) is used as the carrier.
  • CN106140193A discloses a preparation method of a catalyst for hydrodechlorination of CFC and HCFC.
  • the catalyst precursor includes main active components and auxiliary agents, the main active components are Pd and Cu, and the auxiliary agents are selected from transition metals, alkali metals, alkaline earths One, two or more combinations of metals and rare earth metals.
  • the auxiliary agent is selected from one, two or a combination of three or more of Mg, Ca, Ba, Co, Mo, Ni, Sm and Ce.
  • the main active ingredients and auxiliary agents are supported on a carrier, and the carrier is preferably activated carbon, aluminum fluoride or aluminum oxide.
  • CN105457651 discloses a hydrodechlorination catalyst, which consists of a main catalyst, an auxiliary agent and a carrier; the main catalyst is Pd and Cu; the auxiliary agent is selected from one of Mg, Ca, Ba, Co, Mo, Ni, Sm and Ce One, two or three or more combinations; the main catalyst and the auxiliary agent are supported on the activated carbon carrier. Its preparation method: adding activated carbon into an acid or alkali solution, refluxing in a water bath for 2-4 hours at 60-90 DEG C, washing and drying; using the soluble salt solution of the main catalyst and auxiliary agent used to separate it under vacuum or normal pressure conditions.
  • Step-impregnated or co-impregnated activated carbon drying the impregnated activated carbon at a drying temperature of 90-120°C; reducing the dried activated carbon to obtain a catalyst.
  • a metal alloy phase is formed on the surface of the carrier between the selected first active component and the second active component, and the activity is moderate, which is beneficial to improve product selectivity and prolong catalyst life.
  • the raw material conversion rate can reach 97.8%, and the CTFE selectivity is up to 96.2%.
  • the hydrodechlorination catalysts in the prior art still have problems such as the conversion rate and selectivity need to be further improved, the catalysts are prone to carbon deposition, and the long-term stability is poor.
  • the present invention proposes two hydrodechlorination catalysts with high stability, high selectivity, not easy to deposit carbon and long service life, which are applied to the hydrodechlorination of trifluorotrichloroethane to produce chlorotrifluoroethylene
  • the reaction has high activity, selectivity and stability.
  • the present invention provides the first hydrodechlorination catalyst, which is specifically as follows:
  • a hydrodechlorination catalyst uses activated carbon as a carrier, the active metal components include Pd and Cu, the auxiliary agent includes Zn, and the mass percentage of the active metal components is 0.5-3% based on the total weight of the catalyst, It is preferably 0.5-2%, more preferably 0.6-1%, the mass percentage of the auxiliary agent is 0.2-2%, preferably 0.4-1%, more preferably 0.6-0.8%, and the specific surface area of the catalyst is 800-1500m 2 /g, the total acid content of the catalyst is 0.2-1.5 mmol/g, preferably 0.4-1.2 mmol/g.
  • the acid strength of the catalyst is -5.6 ⁇ H 0 ⁇ -3.0, the acid content is ⁇ 90%, the acid content is 0-10% within the range of H 0 ⁇ -5.6, and the acid content is within the range of H 0 >-3.0. 0-10%.
  • the catalyst acid strength was measured by n-butylamine titration.
  • the amount of acid in the range of acid strength of the catalyst -5.6 ⁇ H 0 ⁇ -3.0 is ⁇ 95%
  • the amount of acid in the range of H 0 ⁇ -5.6 accounts for 0-5%
  • the amount of acid in the range of H 0 >-3.0 The proportion is 0-5%.
  • the ratio of catalyst B acid/L acid center is 1:(5-50), preferably 1:(10-40), more preferably 1:(20-35).
  • the ratio of Catalyst B acid/L acid sites was measured by pyridine adsorption.
  • the amount of acid B and acid L of the catalyst of the present invention is controlled within an appropriate range, so that the hydrodechlorination capacity of the catalyst is improved.
  • the mass ratio of Pd and Cu is (1-7):(1-4).
  • the catalyst activated carbon carrier is pretreated activated carbon obtained by sequentially treating with hydrofluoric acid and ammonia water.
  • the auxiliary agent of the present invention is more concentrated on the catalyst surface.
  • the high abundance of Zn atoms on the catalyst surface adjusted the acidity of the catalyst surface and enhanced the anti-carbon deposition performance.
  • the abundance of Zn atoms on the catalyst surface reaches 60-90 wt%, preferably 70-85 wt%.
  • the atomic mass ratio of Pd/Zn on the catalyst surface was 1:(5-20), and the atomic mass ratio of Cu/Zn was 1:(5-20).
  • the average pore size of the catalyst measured by mercury porosimetry is 2-10 nm, preferably 4-8 nm.
  • the pores of the catalyst with a diameter of 5-10 nm account for 50-80% of the total pore volume, preferably 60-75%.
  • the catalyst pore structure is reasonable and the heat transfer effect is good.
  • Hydrodechlorination catalyst is used for hydrodechlorination of trifluorotrichloroethane to produce chlorotrifluoroethylene.
  • the preparation method of the first hydrodechlorination catalyst of the present invention comprises the following steps:
  • the step of pretreating the activated carbon in step (1) includes: adding the activated carbon into a hydrofluoric acid solution with a mass concentration of 5-20%, the mass ratio of activated carbon:hydrofluoric acid solution is 1:(1-2), and at 50-20% Reflux treatment at 100°C for 2-24 hours, washed with deionized water, dried, and then added to ammonia water with a mass concentration of 10-30%, the mass ratio of activated carbon: ammonia water is 1: (1-2), stirring at room temperature for 1-10 hours , washed with deionized water and dried.
  • the pretreated activated carbon of the present invention has improved acid strength distribution, specific surface area and pore structure, high dispersion degree of active components and auxiliary agents on the surface of the carrier, high bonding strength between the carrier and active components and auxiliary agents, and high catalyst activity and stability. Sex is high.
  • the step of supporting the active metal component on the pretreated activated carbon carrier in step (2) includes: adding the pretreated activated carbon carrier to a solution containing soluble Pd salt and soluble Cu salt, and immersing it for 2-24 hours, Wash and dry.
  • the soluble Pd salt is selected from palladium chloride, palladium nitrate and the like.
  • the soluble Cu salt is selected from copper chloride, copper nitrate and the like.
  • the molar concentration of the soluble Pd salt is 1-2 mol/L
  • the molar concentration of the soluble Cu salt is 1-2 mol/L
  • the step of introducing the auxiliary component in step (3) includes: adding the carrier carrying the active metal component into the zinc acetate aqueous solution with a mass percentage of 5-20%, and immersing it at 60-80 ° C for 2-8 hours, It is then filtered and dried under vacuum at 80-100°C for 6-24 hours.
  • the roasting step in step (4) includes: roasting in a nitrogen atmosphere at a temperature of 250-500° C. for 2-5 hours, and then roasting at a temperature of 150-300° C. in a hydrogen atmosphere for 1-3 hours.
  • the heating rate when rising from room temperature to 300-500 DEG C is 20-50 DEG C/min, and the temperature is naturally lowered to room temperature after the roasting.
  • the heating rate from room temperature to 150-300 °C is 10-20 °C/min, and the temperature is naturally lowered to room temperature after the calcination.
  • the control of the roasting process of the present invention further adjusts the size and distribution of the catalyst specific surface area, the catalyst acid content and the acid strength, promotes the conversion of the B acid center to the L acid center, and the distribution of the acid sites is uniform.
  • the hydrodechlorination of trifluorotrichloroethane to chlorotrifluoroethylene is a strong exothermic process, and carbon deposition is the main reason for the deactivation of the hydrodechlorination catalyst.
  • the invention reduces the carbon deposition active center of the catalyst, makes the catalyst less prone to carbon deposition, suppresses the occurrence of side reactions, and prolongs the life of the catalyst.
  • the present invention provides a second hydrodechlorination catalyst, which is specifically as follows:
  • a hydrodechlorination catalyst comprising a carrier, a main catalyst and an auxiliary
  • the carrier is activated carbon, Al 2 O 3 or SiO 2 , and the main catalyst and auxiliary agent are supported on the carrier;
  • the main catalysts are Pd and Cu;
  • the amount of Pd accounts for 0.5-3% of the total mass of the catalyst
  • the amount of Cu accounts for 2.0-10.5% of the total mass of the catalyst
  • the amount of the auxiliary agent is 0.2-3.0% of the total mass of the catalyst.
  • the auxiliary agent is Sn and/or Mn, and the amount of Sn and/or Mn accounts for 0.2-3.0% of the total mass of the catalyst.
  • the auxiliary agent in addition to Sn and/or Mn, also includes one to three kinds of Zn, Zr, Ag, Ti, Cd, Hg, In, Pb, and Bi; the amount of the auxiliary agent is the total mass of the catalyst 0.2-3.0%, and the amount of Sn and/or Mn accounts for 0.1-2.0% of the total mass of the catalyst.
  • the addition of Zn, Zr, Ag, Ti, Cd, Hg, In, Pb, Bi and other auxiliary components further adjusts the surface properties of the catalyst and improves the dispersion and binding of Sn and/or Mn, Pd, and Cu on the carrier sex.
  • the auxiliary agents are Sn and Zn.
  • the auxiliary agents are Mn and Zn.
  • the auxiliary agent is Sn, Mn, Zn.
  • the auxiliary agent is Sn, Zn, Ti.
  • the auxiliary agent is Mn, Zn, Ti.
  • the auxiliary agent is Sn, Mn, Zn, Ti.
  • the auxiliary agent is Sn, Zr, Cd, Bi.
  • the auxiliary agent is Mn, Zr, Cd, Bi.
  • the auxiliary agent is Sn, Mn, Zr, Cd, Bi.
  • the auxiliary agent is Sn, Ag, Hg, In.
  • the auxiliary agent is Mn, Ag, Hg, In.
  • the auxiliary agent is Sn, Mn, Ag, Hg, In.
  • the preparation method of the catalyst of the present invention comprises: impregnating the carrier in the impregnation liquid of the active component and the auxiliary agent.
  • the active component and auxiliary agent immersion liquid includes active component and auxiliary agent soluble salt; the pH value of the immersion liquid is in the range of 3-9.5. As a further preferred solution, the pH value of the impregnation solution is in the range of 7-9.
  • the soluble salt of the active component and the auxiliary agent can be chloride or nitrate.
  • the carrier is activated carbon
  • the activated carbon is subjected to high temperature pretreatment, acid washing/alkali washing pretreatment before impregnating the active components and auxiliary agents.
  • High temperature pretreatment, acid washing/alkali washing pretreatment can improve the stability of the activated carbon support and the binding ability with the supporting components.
  • the specific surface area of the activated carbon is 800-1500 m 2 /g.
  • nitric acid, hydrochloric acid, sulfuric acid, perchloric acid and hydrofluoric acid are used for pickling pretreatment.
  • high temperature is used to perform high temperature pretreatment on the activated carbon, and the temperature can be set to 1700-2000 °C.
  • High temperature pretreatment time is 2-6 hours, vacuum environment.
  • the present invention also protects a method for preparing chlorotrifluoroethylene, which selects the above hydrodechlorination catalyst, and reacts trifluorotrichloroethane, hydrogen and the hydrodechlorination catalyst at 150-300° C. to obtain trifluorotrifluoroethylene vinyl chloride.
  • reaction pressure is controlled to be 1-1.5MPa.
  • the residence time is controlled to be 15-25s.
  • the hydrogen gas velocity is 30-60ml/min.
  • the molar ratio of hydrogen to trifluorotrichloroethane is (1.5-3.1):1.
  • the raw material space velocity is 10-1300h -1 , more preferably 10-1100h -1 .
  • the beneficial effects of the present invention include:
  • Both of the two hydrodechlorination catalysts of the present invention have the advantages of good stability, high activity, high reaction selectivity, friendly applicable reaction temperature, long service life, etc.
  • When used in the preparation of chlorotrifluoroethylene it can realize green environmental protection, The beneficial effect of cost reduction is more conducive to industrial scale production.
  • the first hydrodechlorination catalyst of the present invention reduces the carbon deposit active center of the catalyst by adjusting the acidity, pore structure, etc. of the catalyst, so that the catalyst is not easy to deposit carbon, suppresses the occurrence of side reactions, and prolongs the catalyst life. life.
  • the second hydrodechlorination catalyst of the present invention is based on the Pd-Cu system catalyst, and Sn or Mn is added to suppress the agglomeration and improve the catalyst performance.
  • Sn or Mn is added to suppress the agglomeration and improve the catalyst performance.
  • the activated carbon was added to the hydrofluoric acid solution with a mass concentration of 20%, the mass ratio of activated carbon: hydrofluoric acid solution was 1:2, refluxed at 80 ° C for 10 hours, washed with deionized water, dried, and then added with a mass concentration of 28%.
  • the mass ratio of activated carbon: ammonia water is 1:2, stirring at room temperature for 5 hours, washing with deionized water, and drying.
  • the pretreated activated carbon support was added to a solution containing palladium chloride and cupric chloride, soaked for 6 hours, washed and dried.
  • the molar concentration of palladium chloride is 1 mol/L
  • the molar concentration of cupric chloride is 1 mol/L.
  • the carrier carrying the active component was added to a zinc acetate aqueous solution with a mass percentage of 10%, immersed at 70° C. for 6 hours, then filtered and vacuum-dried at 80° C. for 12 hours. Under a nitrogen atmosphere, the temperature was increased from room temperature to 400 °C at a heating rate of 20 °C/min, and calcined at 400 °C for 3 hours, then naturally lowered to room temperature, switched to a hydrogen atmosphere, and the temperature was increased from room temperature at a heating rate of 15 °C/min. Raised to 250°C and calcined at 250°C for 2 hours, then naturally cooled to room temperature.
  • Pd is 0.5wt%
  • Cu is 1wt%
  • Zn is 1wt%
  • the specific surface area of the catalyst is 882m 2 /g
  • the total acid content of the catalyst is 1.1mmol/g.
  • the acid strength of the catalyst measured by n-butylamine titration method is 95% in the range of -5.6 ⁇ H 0 ⁇ -3.0
  • the proportion of acid in the range of H 0 ⁇ -5.6 is 2%
  • the proportion of acid inside is 3%.
  • the ratio of catalyst B acid/L acid sites measured by pyridine adsorption was 1:20.
  • the abundance of Zn atoms on the catalyst surface reaches 75wt%.
  • the atomic mass ratio of Pd/Zn on the catalyst surface was 1:7.5, and the atomic mass ratio of Cu/Zn was 1:5.
  • the average pore size of the catalyst measured by mercury porosimetry was 5.8 nm.
  • the catalyst pores with a diameter of 5-10 nm accounted for 64% of the total pore volume.
  • the prepared catalyst catalyzes the reaction of trifluorotrichloroethane and hydrogen under the conditions of a reaction temperature of 300°C, a space velocity of 300h -1 and a molar ratio of trifluorotrichloroethane to hydrogen of 1:3, trifluorotrichloroethane will react with hydrogen.
  • the conversion rate of ethane reaches 100%, and the selectivity of chlorotrifluoroethylene reaches 99.46%.
  • the conversion rate of trifluorotrichloroethane was still 100%, and the selectivity of trifluorochloroethylene was 99.38%.
  • the activated carbon was directly loaded with active metal components without pretreatment.
  • the specific surface area of the catalyst was 554 m 2 /g, and the total acid content of the catalyst was 1 mmol/g.
  • the acid strength of the catalyst measured by n-butylamine titration method is 81% in the range of -5.6 ⁇ H 0 ⁇ -3.0, the acid content in the range of H 0 ⁇ -5.6 is 6%, and the range of H 0 >-3.0
  • the proportion of acid inside is 13%.
  • the ratio of catalyst B acid/L acid sites measured by pyridine adsorption was 1:73.
  • the abundance of Zn atoms on the catalyst surface reaches 53wt%.
  • the atomic mass ratio of Pd/Zn on the catalyst surface was 1:3, and the atomic mass ratio of Cu/Zn was 1:2.
  • the average pore size of the catalyst measured by mercury porosimetry was 2.5 nm.
  • the catalyst pores with a diameter of 5-10 nm accounted for 38% of the total pore volume.
  • the prepared catalyst catalyzes the reaction of trifluorotrichloroethane and hydrogen under the conditions of a reaction temperature of 300°C, a space velocity of 300h -1 and a molar ratio of trifluorotrichloroethane to hydrogen of 1:3, trifluorotrichloroethane will react with hydrogen.
  • the ethane conversion was 100% and the chlorotrifluoroethylene selectivity was 97.24%.
  • the conversion rate of trifluorotrichloroethane was 98.45%, and the selectivity of chlorotrifluoroethylene was 93.78%.
  • Example 1.1 no auxiliary Zn was added.
  • the specific surface area of the catalyst was 875 m 2 /g, and the total acid content of the catalyst was 2.1 mmol/g.
  • the acid strength of the catalyst measured by n-butylamine titration method is 79% in the range of -5.6 ⁇ H 0 ⁇ -3.0, the acid content in the range of H 0 ⁇ -5.6 is 15%, and the range of H 0 >-3.0
  • the proportion of acid inside is 6%.
  • the ratio of Catalyst B acid/L acid sites measured by pyridine adsorption was 2:1.
  • the average pore size of the catalyst measured by mercury porosimetry was 6.3 nm. The catalyst pores with a diameter of 5-10 nm accounted for 52% of the total pore volume.
  • the prepared catalyst catalyzes the reaction of trifluorotrichloroethane and hydrogen under the conditions of a reaction temperature of 300°C, a space velocity of 300h -1 and a molar ratio of trifluorotrichloroethane to hydrogen of 1:3, trifluorotrichloroethane will react with hydrogen.
  • the ethane conversion was 100% and the chlorotrifluoroethylene selectivity was 96.49%.
  • the conversion rate of trifluorotrichloroethane was 97.73%, and the selectivity of chlorotrifluoroethylene was 92.46%.
  • the specific surface area of activated carbon is 910m 2 /g.
  • the carrier was immersed in the impregnation solution, immersed at 60°C for 2 hours, and then dried at 90°C for 12 hours.
  • the catalyst was reduced by hydrogen at 200 °C for 2 h before use.
  • the catalyst prepared in Example 2.2 is carried out to the hydrodechlorination of trichlorotrichloroethane, and the catalytic reaction temperature is controlled to be 280 ° C and then feed hydrogen and trichlorotrichloroethane, and the mol ratio of hydrogen and trichlorotrichloroethane It is 1.8:1, the reaction pressure is 1.1Mpa, the residence time is 20 seconds, the hydrogen gas velocity is 40ml/min, and the raw material space velocity is 500h -1 .
  • the reaction product is subjected to rapid cooling, alkali washing, water washing, drying, compression and rectification to obtain chlorotrifluoroethylene,

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Abstract

La présente invention concerne deux catalyseurs d'hydrodéchloration et leur application dans la préparation de chlorotrifluoroéthylène. Le catalyseur d'hydrodéchloration comprend un support, un constituant actif et un agent auxiliaire. Un premier catalyseur d'hydrodéchloration prend du charbon actif en tant que support, le constituant métallique actif comprend du Pd et du Cu, et l'agent auxiliaire comprend du Zn ; en prenant le poids total du catalyseur en tant que référence, la teneur en pourcentage en masse du constituant métallique actif est de 0,5 à 3 %, et la teneur en pourcentage en masse de l'agent auxiliaire est de 0,2 à 2 %. Le support d'un second catalyseur d'hydrodéchloration est du charbon actif, Al2O3 ou SiO2, un catalyseur principal et l'agent auxiliaire sont chargés sur le support, le catalyseur principal comprend du Pd et du Cu, et l'agent auxiliaire comprend Sn et/ou Mn. Les catalyseurs selon la présente invention présentent une bonne stabilité, une sélectivité de réaction élevée, moins de dépôt de carbone et une longue durée de vie en service, et est plus bénéfique pour la production à l'échelle industrielle lorsqu'elle est utilisée pour la préparation de chlorotrifluoroéthylène.
PCT/CN2021/117090 2020-12-10 2021-09-08 Catalyseur d'hydrodéchloration et son application dans la préparation de chlorotrifluoroéthylène WO2022121398A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
CN202011454875.0A CN112495394A (zh) 2020-12-10 2020-12-10 一种加氢脱氯催化剂及三氟氯乙烯的制备方法
CN202011453854.7A CN112547093B (zh) 2020-12-10 2020-12-10 一种加氢脱氯催化剂及其制备方法和应用
CN202011453854.7 2020-12-10
CN202011454875.0 2020-12-10

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116139893A (zh) * 2022-12-21 2023-05-23 西安近代化学研究所 选择性加氢脱氯合成三氟乙烯催化剂及三氟乙烯制备方法

Citations (6)

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Publication number Priority date Publication date Assignee Title
EP0416615A1 (fr) * 1989-09-06 1991-03-13 Daikin Industries, Limited Procédé pour la préparation de chlorotrifluoroéthylène
CN102211028A (zh) * 2010-04-08 2011-10-12 中化蓝天集团有限公司 合成三氟乙烯用加氢脱氯催化剂和其载体的新型预处理工艺
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