WO1999056873A1 - Procede permettant de produire des alcools fluores - Google Patents

Procede permettant de produire des alcools fluores Download PDF

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Publication number
WO1999056873A1
WO1999056873A1 PCT/JP1999/002166 JP9902166W WO9956873A1 WO 1999056873 A1 WO1999056873 A1 WO 1999056873A1 JP 9902166 W JP9902166 W JP 9902166W WO 9956873 A1 WO9956873 A1 WO 9956873A1
Authority
WO
WIPO (PCT)
Prior art keywords
catalyst
reaction
formula
producing
potassium
Prior art date
Application number
PCT/JP1999/002166
Other languages
English (en)
Japanese (ja)
Inventor
Jun Miki
Hirokazu Aoyama
Original Assignee
Daikin Industries, Ltd.
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 Daikin Industries, Ltd. filed Critical Daikin Industries, Ltd.
Publication of WO1999056873A1 publication Critical patent/WO1999056873A1/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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
    • B01J23/04—Alkali metals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/09—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis
    • C07C29/12—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of esters of mineral acids
    • C07C29/124—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of esters of mineral acids of halides

Definitions

  • the present invention relates to a method for producing fluoroalcohol and a catalyst used in the method.
  • An object of the present invention is to produce fluoroalcohol in a high yield under mild reaction conditions and without using any special reagent or solvent.
  • the present invention provides the following catalysts and a method for producing fluoroalcohol.
  • Item 1 A catalyst for producing a fluoroalcohol comprising a metal component supported on a solid acid.
  • Item 2. The catalyst according to Item 1, wherein the solid acid is a Si-A1 or A1-P complex oxide.
  • Item 3. The catalyst according to Item 1, wherein the solid acid is a Lewis acid.
  • Item 4 The catalyst according to Item 1, wherein the metal component of aluminum is potassium, potassium oxide, potassium hydroxide, potassium salt, or a mixture of two or more thereof.
  • R f represents a perfluoroalkoxy group or a polyfluoroalkyl group.
  • n shows the integer of 1-5.
  • X represents I, 81 "or (1.]
  • R f represents a perfluoroalkyl group or a polyfluoroalkyl group.
  • n shows the integer of 1-5.
  • X represents I, 81 "or (1.)
  • the catalyst of the present invention is a solid acid catalyst for producing a fluoroalcohol, which comprises an alkali metal supported on a solid acid.
  • Metal sulfates (nickel sulfate, iron sulfate, etc.);
  • Solidified acid (phosphoric acid Z silica, SbF 5 Z silica, BF 3 / C, etc.),
  • Natural minerals and layered compounds activated clay, natural zeolite, etc.
  • heteropoly acid such as H 3 PW 12 O 4 ⁇ 5 H 2 0, H3PW12O40 ⁇ 6 H 2 0.
  • Preferred solid acids include silica'alumina and silica-alumina-based synthetic zeolite, or aluminum phosphate and phosphoric acid-alumina-based synthetic zeolite, or 'alumina-phosphate'silica-based synthetic zeolite.
  • the production of the catalyst of the present invention in which the metal component is supported on the surface of the solid acid carrier is performed by a sol-gel method, an impregnation method, a coprecipitation method, a CVD method (chemical vapor deposition) which has been conventionally used as a catalyst preparation method. Method), any method such as an ion implantation method can be adopted.
  • a sol-gel method an impregnation method, a coprecipitation method, a CVD method (chemical vapor deposition) which has been conventionally used as a catalyst preparation method. Method
  • any method such as an ion implantation method can be adopted.
  • zeolite is used as the solid acid
  • the zeolite is impregnated with a soluble alkali metal compound solution (for example, an aqueous solution of alkali metal hydroxide or alkali metal salt), and then calcined if necessary. Can be obtained.
  • a soluble alkali metal compound solution for example, an aqueous solution
  • soluble metal compounds such as alkali metal (Na, K) salts such as tungstate, zirconate, germanate, niobate, tantalate, molybdate, hafnate, vanadate, zincate, stannate, and aluminate
  • alkaline earth metal salts halides (chlorides, bromides, iodides, fluorides) of various metals, sulfates, nitrates, alkoxides, hydroxides, organic acid salts (eg, acetate), ammonium salts, etc.
  • a solid containing an alkali metal is prepared from a mixed solution to which a soluble alkali metal compound is added, if necessary, and the solid is calcined, if necessary, to convert the alkali metal into a solid acid.
  • a supported catalyst can be obtained.
  • the calcination can be performed at 200 to 700 ° C, preferably 300 to 500 ° C, in an air or oxygen atmosphere.
  • the ratio of the alkali metal component in the total catalyst are alkali metal oxides as (Na 2 0, K 2 0 , L i 2 0, Rb 2 0, C s 2 0), about 1 to 30 wt%, preferably from 5 About 17% by weight.
  • the shape of the solid acid when impregnated with the alkali metal compound solution may be in the form of powder, granules, tablets, or honeycomb, and is not particularly limited.
  • the perfluoroalkyl group includes a linear or branched perfluoroalkyl group having 1 to 20 carbon atoms, for example, CF 3 , C 2 F 5 , CaF 7 (n—, iso) C 4 F 9 (n—, iso, sec—, tert—) and CF 3 (CF 2 ) m — (m represents an integer of 4 to 19) are exemplified.
  • Examples of the polyfluoroalkyl group include HCF 2 (CF 2 ) p ⁇ (p is an integer of 1 to 19).
  • the solvation reaction is a reaction in which a halogenated fluorine compound and water are used as raw materials to produce an alcohol by a batch reaction or a continuous reaction.
  • the preferable production conditions are to use the catalyst of the present invention at a reaction temperature of 150 to 300 ° C, preferably 200 to 240 ° C.
  • the reaction pressure is preferably from normal pressure to pressurized.
  • the molar ratio of the halogenated fluorine compound to water is preferably 1: 0.2 to 100.
  • a continuous reactor for a gas phase equipped with a reactor such as a fixed bed, a fluidized bed, or a moving bed, or a batch reactor can be used. .
  • an oxygen-containing gas such as air or a diluent gas thereof in addition to an inert gas such as nitrogen, helium, or carbon dioxide.
  • an inert gas such as nitrogen, helium, or carbon dioxide.
  • SAP 0 (S i 0 2: 6wt%, A 1 2 0 3: 39wt%, P 2 0 5: 52 wt%) 10 g in impregnation aqueous potassium carbonate solution 30 cc (5 wt% as K 2 0) The mixture was heated in a hot water bath and dried. Furthermore, it was calcined in a Matsufuru furnace at 400 times for 3 hours and used for the reaction.
  • a stainless steel reaction tube having an inner diameter of 1 Omm and a length of 250 mm was filled with 2.5 g of the catalyst of Production Example 1, and heated to 215 ° C with a heater.
  • this reaction tube
  • CF 3 CF 2 (CF 2 CF 2 ) 3 CH 2 CH 2 I and water were supplied at 10 gZhr and 12 gZhr, respectively, and were subjected to a catalytic reaction on the catalyst.
  • the reaction product was collected using an ice trap attached to the outlet of the reaction tube and a dry ice methanol trap, and subjected to GC analysis. Table 1 shows the results.
  • an alcohol or ether compound can be selectively obtained with less olefin (by-product) due to a dehydrogenogenation reaction.

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

Abstract

L'invention concerne des catalyseurs qui permettent de produire des alcools fluorés renfermant un composant métal alcalin porté par un acide solide, ainsi qu'un procédé qui permet de produire des alcools fluorés.
PCT/JP1999/002166 1998-05-07 1999-04-22 Procede permettant de produire des alcools fluores WO1999056873A1 (fr)

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
JP12454198 1998-05-07
JP10/124541 1998-05-07
JP10/194617 1998-07-09
JP19461798 1998-07-09
JP32836798A JP4203687B2 (ja) 1998-05-07 1998-11-18 フッ素アルコール製造用触媒及び該触媒を用いたフッ素化合物の製造方法
JP10/328367 1998-11-18

Publications (1)

Publication Number Publication Date
WO1999056873A1 true WO1999056873A1 (fr) 1999-11-11

Family

ID=27314948

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP1999/002166 WO1999056873A1 (fr) 1998-05-07 1999-04-22 Procede permettant de produire des alcools fluores

Country Status (2)

Country Link
JP (1) JP4203687B2 (fr)
WO (1) WO1999056873A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1224971A1 (fr) * 1999-05-12 2002-07-24 Daikin Industries, Ltd. Catalyseurs pour la preparation d'alcools fluores et procede de preparation d'alcools fluores

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4599780B2 (ja) * 2001-09-13 2010-12-15 ダイキン工業株式会社 含フッ素アルコール化合物の製造用触媒及び含フッ素アルコールの製造方法

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62238223A (ja) * 1986-04-04 1987-10-19 ヘキスト　アクチェンゲゼルシャフト 弗素含有多価アルコ−ル、その製造方法およびその用途
JPS62273925A (ja) * 1986-05-23 1987-11-28 Asahi Chem Ind Co Ltd ２，２−ジフルオロエタノ−ルの製造方法

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62238223A (ja) * 1986-04-04 1987-10-19 ヘキスト　アクチェンゲゼルシャフト 弗素含有多価アルコ−ル、その製造方法およびその用途
JPS62273925A (ja) * 1986-05-23 1987-11-28 Asahi Chem Ind Co Ltd ２，２−ジフルオロエタノ−ルの製造方法

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1224971A1 (fr) * 1999-05-12 2002-07-24 Daikin Industries, Ltd. Catalyseurs pour la preparation d'alcools fluores et procede de preparation d'alcools fluores
EP1224971A4 (fr) * 1999-05-12 2004-09-08 Daikin Ind Ltd Catalyseurs pour la preparation d'alcools fluores et procede de preparation d'alcools fluores

Also Published As

Publication number Publication date
JP4203687B2 (ja) 2009-01-07
JP2000079345A (ja) 2000-03-21

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