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WO1997010053A1 - Catalyseur pour la fluoration d'hydrocarbure halogene - Google Patents

Catalyseur pour la fluoration d'hydrocarbure halogene Download PDF

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Publication number
WO1997010053A1
WO1997010053A1 PCT/CN1996/000061 CN9600061W WO9710053A1 WO 1997010053 A1 WO1997010053 A1 WO 1997010053A1 CN 9600061 W CN9600061 W CN 9600061W WO 9710053 A1 WO9710053 A1 WO 9710053A1
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WO
WIPO (PCT)
Prior art keywords
content
catalyst
fluorination
hydrogen fluoride
nitrogen
Prior art date
Application number
PCT/CN1996/000061
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English (en)
Chinese (zh)
Inventor
Jian Lu
Hengdao Quan
Huifang Li
Hui'e Yang
Zhenyu Wang
Zhong Li
Lei Shi
Hongxiang Qu
Zhixia Zhao
Jie Li
Zhongzhang Hao
Huili Li
Original Assignee
Xi'an Institute Of Modern Chemistry
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Xi'an Institute Of Modern Chemistry filed Critical Xi'an Institute Of Modern Chemistry
Publication of WO1997010053A1 publication Critical patent/WO1997010053A1/fr

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Classifications

    • 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
    • B01J27/132—Halogens; Compounds thereof with chromium, molybdenum, tungsten or polonium
    • 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
    • B01J27/125—Halogens; Compounds thereof with scandium, yttrium, aluminium, gallium, indium or thallium
    • 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
    • C07C17/20—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms
    • C07C17/21—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms with simultaneous increase of the number of halogen atoms

Definitions

  • the invention relates to a fluorination catalyst, which is mainly used for the gas-phase fluorination reaction of halogenated hydrocarbons and hydrogen fluoride. Background technique
  • R-134a 1, 1, 1, 2-tetrafluoroethane
  • the fluorination catalyst used is Cr 2 0 3 / Al 2 0 3 .
  • catalysts such as chromium, fluorine, and oxides are used in the gas phase.
  • Direct trifluoride ethylene is fluorinated. Only 3% of 134a can be obtained.
  • the catalyst's activity rapidly decays, and the catalyst needs to be frequently regenerated. Replacement. Obviously not conducive to industrial production. ⁇
  • EP29 $, 885A1 reports a method for preparing R-134a.
  • the catalyst is a commercial r-Al 2 0 3 carrier (specific surface area> 100m2 g-1), which is impregnated with an active metal compound and then dried in a reaction tube. Fluorinated. All r -Al 2 0 3 fluorinated with HF in the reaction tube is converted into A1F 3 .
  • A-201 has a bulk density of 0.53gml_l and a specific surface area of 325m2 g "l. After being impregnated with the active ingredient, it is dried and fluorinated.
  • EP0408005A1 reports a catalyst preparation method using A1F 3 as a support.
  • the specific surface area of A1F 3 used is only 26tn2 g-1, and the exact crystal phase and composition of its support are not disclosed. It supports a single trivalent chromium compound (CrCl 3 ⁇ 6 ⁇ 2 0), and no other co-catalyst is added, so it is difficult to ensure Optimum catalyst selectivity and stable catalytic activity
  • the crystal phase composition and specific surface area of A1F3 as a gasification catalyst support are closely related to the activity of the catalyst.
  • the supported catalyst has a higher ⁇ content when the content of ⁇ is larger and the specific surface area is larger.
  • A1F 3 is very low.
  • A1F 3 is prepared from Al 2 0 3 by conventional gas phase fluorination, the specific surface area of A1F 3 is greatly reduced due to the strong exothermic reaction. The content of r-crystalline phase and amorphous phase is also greatly reduced.
  • the purpose of the present invention is to overcome the shortcomings of the background technology. Design a fluorination catalyst with a high A1 F 3 content, a large specific surface area, and a large pore volume. The active ingredient is evenly distributed on the support.
  • the catalyst prepared by the traditional method cannot be achieved.
  • the existing method for expanding the specific surface area and pore volume of the carrier is to add carbon black, paraffin, and polyvinyl alcohol as pore-forming agents. When burned, the generated gas can be removed to produce pores.
  • these pore formers must react at a temperature higher than 50 TC. For the r-A1F 3 crystal form. Under such high temperature conditions, grain growth will occur, and r-AlF 3 will change to "-A1F 3 " with a significant decrease in specific surface area.
  • Another method for preparing a pseudo specific surface catalyst is to uniformly precipitate the components required for the catalyst from an aqueous solution.
  • the A1F 3 prepared by this method is powdery, and the mechanical strength after molding is very low, so it has no application value.
  • the pore-forming agent was also removed by fluorination at the same time as the gasification of Al 2 0 3 , which broke the traditional method of high-temperature burning and displacing the pore-forming agent.
  • the use of Si0 2 as a pore-forming agent is based on the characteristics of the chain structure of Si0 2 and the easy reaction with HF to form volatile fluorinated silicon compounds. Once removed by fluorination, it will leave a continuous pore structure, thereby increasing the specific surface area and The pore volume is superior to the existing pore structure of A1F 3 , has a specific surface area of rhenium, a large pore volume, and relatively low mechanical strength.
  • the fluorination catalyst for fluorinated halohydrocarbons is characterized in that r-A1 2 0 3 containing Si0 2 is 3-20%, mixed gas with anhydrous hydrogen fluoride and nitrogen, and pure anhydrous HF, at 150 -Gas-phase fluorination at 300 ° C to drive off A1F 3 carrier as a pore-forming agent with specific surface area
  • the average grain size is ⁇ 15 ⁇ . Dipping method using supported chromium chloride, cobalt and magnesium, which mass ratio of metal ion: 1 to 10: 1: 0.1 cured at 120- 3 5 0 ° C with nitrogen or air and then at 180 350 e C was activated with a mixture of silver hydrogen and nitrogen.
  • the present invention has the following advantages:
  • the carrier A1F 3 has a large specific surface area and pore volume. Suitable pore size distribution.
  • r-A1F 3 supports active components Cr 3+ , Co 2+ , Mg 2+ , and the prepared catalyst enables the fluorination reaction to proceed at a lower temperature. And has the best selectivity. And lasting Catalytic activity.
  • This fluoride catalyst can be used in the fluorine-chlorine exchange reaction of various halogenated hydrocarbons. Best way to achieve invention
  • the resulting A1F 3 carrier was used dipping method supported chromium, cobalt, magnesium metal ions in a weight ratio of 5: 1: 0.1, i.e., 5% Cr3 ten, 13 ⁇ 4 (:. 0 2 + and 0.13 ⁇ 4Mg 2+ nickel reactor, 120 ° C, N 2 Airflow (50ml mm " 1 ;) After 12 hours of treatment, the temperature was raised to 350 ° C at a temperature rise rate of rCmin" 1 and the solidified catalyst was cured for 6 hours. The cured catalyst was passed HF at 180 ° C: N 2
  • Characterized carrier A1F 3 vector measured by the BET low temperature nitrogen adsorption specific surface area A1F 3 to 57 m 2 g "l, a pore volume of 0.25mlg _1, average pore diameter 4 ⁇ .
  • Average grain size is 9 8 A.
  • CC1 2 CHC1 + 3HF CF 3 CH 2 C1 + 2HC1 (1)
  • the Si0 2 103 ⁇ 4 prepared containing the resulting r -Al 2 0 3 carrier fluorinated A1F 3 a specific surface area of 50m 2 g- 1, pore volume 0.23mlg- 1 , having an average pore diameter - A1F 3 is 873 ⁇ 4, A1F 3 content of 95% and an average grain size of 105A.
  • the loaded active components still contain: Cr 3 105%> Co 2 10 13 ⁇ 4, Mg 2+ 0.1% »
  • the above catalyst is used in reaction (2).
  • the contact time is 5.35, the conversion is 213 ⁇ 4 and the selectivity is 993 ⁇ 4.
  • the carrier A1F 3 is still dominated by crystalline phase, and the average grain size is still 105A.
  • the content of A1F 3 is ⁇ 3 ⁇ 4.
  • the average grain size is 110A.
  • the conversion rate of TCE was 94%, and the selectivity to R_133a was 993 ⁇ 4.
  • the conversion of TCE was 98%, and the selectivity to R-133a was 993 ⁇ 4.
  • the above catalyst was used in reaction (2).
  • the contact time is 8.2s, the conversion is 22% and the selectivity is 993 ⁇ 4; when the contact time is 5.3s, the conversion is 193 ⁇ 4 and the selectivity is 993 ⁇ 4.
  • the above catalyst is used in reaction (2).
  • contact time is 16.4s
  • R- 133a conversion rate is 25%
  • selectivity is 993 ⁇ 4; when contact time is 8.2s, conversion Rate
  • the selectivity is 993 ⁇ 4; when the contact time is 5.3s, the conversion rate is 13%, and the selectivity is 993 ⁇ 4.
  • 10 1: 0.1, that is, 103 ⁇ 4Cr 3+ , l3 ⁇ 4Co 2 ten, 0.1% g 2+ .

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne un catalyseur pour la fluoration d'hydrocarbure halogéné, qui consiste en un support sur lequel des composés actifs ont été déposés. Ledit support est de l'AlF3 actif préparé par fluoration d'alumine gamma contenant du dioxyde de silicium (SiO2) à 150-300 °C avec un mélange de fluorure d'hydrogène anhydre et d'azote. Lesdits composés actifs contiennent du chrome, du cobalt et du magnésium dans les proportions suivantes: Cr:Co:Mg=1-10:1 0,1 (rapport pondéral). Le catalyseur est fabriqué par imprégnation dudit AlF3 actif d'une solution de chlorures de Cr, Co et Mg. Le catalyseur qui est utile dans la fluoration du trichloréthylène en phase vapeur pour former R-134a, présente une activité et une sélectivité puissantes et une longue durée de vie.
PCT/CN1996/000061 1995-09-13 1996-08-09 Catalyseur pour la fluoration d'hydrocarbure halogene WO1997010053A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN95115476A CN1041804C (zh) 1995-09-13 1995-09-13 氟化卤代烃的氟化催化剂
CN95115476.1 1995-09-13

Publications (1)

Publication Number Publication Date
WO1997010053A1 true WO1997010053A1 (fr) 1997-03-20

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Application Number Title Priority Date Filing Date
PCT/CN1996/000061 WO1997010053A1 (fr) 1995-09-13 1996-08-09 Catalyseur pour la fluoration d'hydrocarbure halogene

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CN (1) CN1041804C (fr)
WO (1) WO1997010053A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0879790A1 (fr) * 1997-05-22 1998-11-25 Ausimont S.p.A. Procédé de préparation de fluorure d'aluminium
EP0879808A3 (fr) * 1997-05-22 1999-05-19 Ausimont S.p.A. Procédé de fluoration de composés organiques halogènes
EP0955266A1 (fr) * 1998-05-07 1999-11-10 Ausimont S.p.A. Procede pour la production de fluorure d'aluminium
US9771309B2 (en) 2005-04-08 2017-09-26 Mexichem Amanco Holding S.A. De C.V. Chromia based fluorination catalyst

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1911512B (zh) * 2005-07-07 2011-12-07 独立行政法人产业技术综合研究所 氟化催化剂及其制备方法、以及使用了该催化剂的氟化合物的制备方法
CN106256429B (zh) * 2015-06-18 2020-02-11 中化近代环保化工(西安)有限公司 一种高比表面积的氟化铝催化剂及其应用
CN105597795B (zh) * 2015-11-06 2018-04-17 西安近代化学研究所 一种纳米氟化铝基催化剂的制备方法
CN106861707B (zh) * 2017-02-09 2019-08-27 西安近代化学研究所 一种氯化氢氧化制氯气催化剂的制备方法
CN106861714B (zh) * 2017-02-09 2019-08-27 西安近代化学研究所 一种氯化氢转化制氯气的催化剂
CN106964402A (zh) * 2017-04-14 2017-07-21 张玲 一种氟化氢活化催化剂的制备方法
CN107597096B (zh) * 2017-08-22 2018-12-04 乳源东阳光氟有限公司 一种以氧化铝为载体的铬基催化剂及其制备方法
CN108273556B (zh) * 2018-01-31 2020-07-21 中国民航大学 一种基于mof的氟/氯交换催化剂的制备方法
CN113856707A (zh) * 2021-09-18 2021-12-31 深圳市东有新材料科技有限公司 一种高催化效率的中空纳米氟化铝球及其制备方法

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN86107751A (zh) * 1985-11-15 1987-05-20 阿托化学公司 由二氯四氟乙烷与氢氟酸合成氯五氟乙烷的方法
EP0408005B1 (fr) * 1989-07-12 1994-03-02 AUSIMONT S.p.A. Procédé pour préparer du 1,1,1,2-tétrafluoroéthane

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN86107751A (zh) * 1985-11-15 1987-05-20 阿托化学公司 由二氯四氟乙烷与氢氟酸合成氯五氟乙烷的方法
EP0408005B1 (fr) * 1989-07-12 1994-03-02 AUSIMONT S.p.A. Procédé pour préparer du 1,1,1,2-tétrafluoroéthane

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0879790A1 (fr) * 1997-05-22 1998-11-25 Ausimont S.p.A. Procédé de préparation de fluorure d'aluminium
EP0879808A3 (fr) * 1997-05-22 1999-05-19 Ausimont S.p.A. Procédé de fluoration de composés organiques halogènes
US6187280B1 (en) * 1997-05-22 2001-02-13 Ausimont S.P.A. Process for the preparation of aluminum fluoride
EP0955266A1 (fr) * 1998-05-07 1999-11-10 Ausimont S.p.A. Procede pour la production de fluorure d'aluminium
US6436362B1 (en) * 1998-05-07 2002-08-20 Ausimont S.P.A. Process for preparing aluminum fluoride
US9771309B2 (en) 2005-04-08 2017-09-26 Mexichem Amanco Holding S.A. De C.V. Chromia based fluorination catalyst
US10189757B2 (en) 2005-04-08 2019-01-29 Mexichem Amanco Holding S.A. De C.V. Chromia based fluorination catalyst

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Publication number Publication date
CN1145275A (zh) 1997-03-19
CN1041804C (zh) 1999-01-27

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