CN117597322A - Process for producing olefin - Google Patents

Process for producing olefin Download PDF

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Publication number
CN117597322A
CN117597322A CN202280047528.7A CN202280047528A CN117597322A CN 117597322 A CN117597322 A CN 117597322A CN 202280047528 A CN202280047528 A CN 202280047528A CN 117597322 A CN117597322 A CN 117597322A
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catalyst
octafluoro
butene
reaction
olefin
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江藤友亮
中村新吾
松永隆行
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Daikin Industries Ltd
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Daikin Industries Ltd
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    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
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    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/12—Silica and alumina
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    • 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
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    • B01J23/26—Chromium
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    • 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
    • B01J23/74—Iron group metals
    • B01J23/745—Iron
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
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    • 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
    • C07C17/358—Preparation of halogenated hydrocarbons by reactions not affecting the number of carbon or of halogen atoms in the reaction by isomerisation
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Abstract

The technical problems to be solved by the invention are as follows: by isomerization, olefins having 4 or more carbon atoms and a double bond at the 2-position are produced. The method for producing an olefin having 4 or more carbon atoms and a double bond at the 2-position comprises a step of isomerizing an olefin having 4 or more carbon atoms and a double bond at the 1-position in the presence of a Lewis acid catalyst.

Description

Process for producing olefin
Technical Field
The present invention relates to a process for producing an olefin.
Background
Non-patent document 1 discloses a fluoride using an alkali metal, production from 1,2,3, 4-octafluoro-1-butene 1,2,3, 4-octafluoro-2-butene.
Prior art literature
Non-patent literature
Non-patent document 1: journal of Organic Chemistry USSR (English Translation) (1987) vol.23p.1651, ISOMERIC COMPOSITION OF THE PRODUCTS FROM THE REACTION OF POLY-AND perflurooro-1-ALKENES WITH ALKALI-METAL FLUORIDES IN APROTIC SOLVENTS, fileakova, t.i.; kodess, m.i.; peschanskii, n.v.; zapevalov, a.ya.; kolenko, I.P.
Disclosure of Invention
Technical problem to be solved by the invention
The technical problems to be solved by the invention are as follows: by isomerization, olefins having 4 or more carbon atoms and a double bond at the 2-position are produced.
Technical scheme for solving technical problems
The invention comprises the following technical proposal.
A process for producing an olefin having 4 or more carbon atoms and a double bond at the 2-position, which comprises the step of isomerizing an olefin having 4 or more carbon atoms and a double bond at the 1-position in the presence of a Lewis acid catalyst.
The production method according to item 1 above, which is 1,2,3, 4-octafluoro-2-butene (CF) 3 －CF＝CF－CF 3 ) The above production method comprises reacting 1,2,3, 4-octafluoro-1-butene (CF) 2 ＝CF－CF 2 －CF 3 ) And a step of carrying out an isomerization reaction in the presence of a Lewis acid catalyst.
The production method according to item 1 or 2, wherein the step of carrying out the isomerization reaction in a gas phase
Item 4. A composition comprising:
1,2,3, 4-octafluoro-2-butene (CF) 3 －CF＝CF－CF 3 )；
1,2,3, 4-octafluoro-1-butene (CF) 2 ＝CF－CF 2 －CF 3 ) The method comprises the steps of carrying out a first treatment on the surface of the And
octafluorocyclobutane (C-C) 4 F 8 )。
Item 5. The composition according to item 4 above is used as an etching gas, a refrigerant, a heat transfer medium, a deposition gas, a block for organic synthesis, or a cleaning gas.
Effects of the invention
By the present invention, an olefin having 4 or more carbon atoms and a double bond at the 2-position can be efficiently produced by isomerization.
Detailed Description
In the present specification, "containing" is a concept that "includes", "consists essentially of (consist essentially of) and" consists of (constancy of) "are included. In the present specification, when the numerical ranges are denoted by "a to B", a is not less than a and not more than B.
As a result of intensive studies, the inventors of the present invention have found that an olefin having 4 or more carbon atoms and a double bond at the 1-position, preferably 1,2,3, 4-octafluoro-1-butene (CF), which is a starting compound, is produced by conducting a reaction in the presence of a Lewis acid catalyst 2 ＝CF－CF 2 －CF 3 ) The step of carrying out the isomerization reaction can efficiently carry out the isomerization reaction, and can produce an olefin having 4 or more carbon atoms and a double bond at the 2-position, preferably 1,2,3, 4-octafluoro-2-butene (CF) at a high conversion, yield and/or high selectivity 3 －CF＝CF－CF 3 )。
The present invention has been completed based on these findings and further repeated studies.
The present invention includes the following embodiments.
The method for producing an olefin having 4 or more carbon atoms and a double bond at the 2-position of the present invention comprises a step of isomerizing an olefin having 4 or more carbon atoms and a double bond at the 1-position of the olefin in the presence of a Lewis acid catalyst.
The production process of the present invention preferably comprises reacting 1,2,3, 4-octafluoro-1-butene in a Lewis acid catalyst 1,2,3, 4-octafluoro-2-butene in the presence of an isomerization reaction step.
The production method of the present invention preferably includes a step of carrying out the isomerization reaction in a gas phase or a liquid phase.
The composition of the present invention comprises:
1,2,3, 4-octafluoro-2-butene (CF) 3 －CF＝CF－CF 3 )；
1,2,3, 4-octafluoro-1-butene (CF) 2 ＝CF－CF 2 －CF 3 ) The method comprises the steps of carrying out a first treatment on the surface of the And
octafluorocyclobutane (C-C) 4 F 8 )。
The composition of the present invention is preferably used as an etching gas, a refrigerant, a heat transfer medium, a deposition gas, a block for organic synthesis, or a cleaning gas.
The present invention can efficiently carry out an isomerization reaction by satisfying the above conditions, and can produce an olefin having 4 or more carbon atoms and a double bond at the 2-position, preferably 1,2,3, 4-octafluoro-2-butene, with high conversion, yield and/or high selectivity.
In the present invention, the "conversion" means a ratio (mol%) of the total molar amount of compounds (olefins having 4 or more carbon atoms and having a double bond at the 2-position, etc.) other than the raw material compounds contained in the gas flowing out from the outlet of the reactor relative to the molar amount of the raw material compounds (olefins having 4 or more carbon atoms and having a double bond at the 1-position) supplied into the reactor.
In the present invention, the term "selectivity" means a ratio (mol%) of the total molar amount of the target compounds (olefins having 4 or more carbon atoms and having double bonds at the 2-position) contained in the gas flowing out from the reactor outlet relative to the total molar amount of the compounds other than the raw material compounds (olefins having 4 or more carbon atoms and having double bonds at the 2-position, etc.) in the flowing gas.
The process for producing an olefin according to the present invention can efficiently carry out an isomerization reaction of an olefin having 4 or more carbon atoms and a double bond at the 1-position in the presence of a Lewis acid catalyst, and can produce an olefin having 4 or more carbon atoms and a double bond at the 2-position with high conversion, yield and/or high selectivity.
(1) Raw material compound
The starting compound of the present invention is an olefin having 4 or more carbon atoms and a double bond at the 1-position.
The olefin of the feed compound is preferably a perfluoroolefin. The perfluoroolefin is an olefin having a perfluoroalkyl group in which all hydrogen atoms are replaced with fluorine atoms.
The olefin of the starting compound preferably has a perfluoroalkyl group.
Perfluoroalkyl is an alkyl group in which all hydrogen atoms are replaced with fluorine atoms. The perfluoroalkyl group is preferably a perfluoroalkyl group having 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, still more preferably 1 to 6 carbon atoms, particularly preferably 1 to 4 carbon atoms, and most preferably 1 to 3 carbon atoms.
The perfluoroalkyl group is preferably a linear or branched perfluoroalkyl group.The perfluoroalkyl group is preferably trifluoromethyl (CF) 3 (-) and pentafluoroethyl (C) 2 F 5 －)。
The number of carbon atoms of the olefin of the starting compound is preferably 4 to 8, more preferably 4, from the viewpoint that the isomerization reaction can be efficiently performed and the olefin of the target compound is produced at a high conversion, yield and/or high selectivity, preferably 1,2,3, 4-octafluoro-2-butene.
The olefin of the starting compound is preferably 1,2,3, 4-octafluoro-1-butene.
The olefins having 4 or more carbon atoms and a double bond at the 1-position in the starting compound may be used alone or in combination of 2 or more kinds. Commercially available olefins may also be used.
(2) Isomerization reaction
In the step of the isomerization reaction of the present invention, an olefin having 4 or more carbon atoms and a double bond at the 1-position is isomerized using a Lewis acid catalyst as a catalyst.
In the step of the isomerization reaction, the olefin of the starting compound is preferably a compound having 4 carbon atoms (C) 4 Compounds) to compounds having 8 carbon atoms (C 8 Compounds), more preferably C 4 A compound.
The step of the isomerization reaction uses a Lewis acid catalyst, and the olefin of the starting compound is preferably 1,2,3, 4-octafluoro-1-butene, the olefin of the target compound is 1,2,3, 4-octafluoro-2-butene.
Lewis acid catalyst (fluorination catalyst or non-fluorination catalyst)
The step of the isomerization reaction of the present invention is a step of isomerizing an olefin of a raw material compound using a Lewis acid catalyst as a catalyst to produce an isomerized compound having 4 or more carbon atomsOlefins having a double bond in the 2-position (preferably 1,2,3, 4-octafluoro-2-butene (CF) 3 －CF＝CF－CF 3 ))。
The isomerization step is preferably performed in the gas phase.
The isomerization step preferably uses a fluorinated lewis acid catalyst or a non-fluorinated lewis acid catalyst as the catalyst.
The lewis acid catalyst is preferably an aluminum chloride catalyst, a chromium oxide catalyst, an aluminum oxide catalyst, a silica aluminum oxide catalyst, a zeolite catalyst, or the like. Regarding the lewis acid catalyst, both non-fluorinated lewis acid catalysts and fluorinated lewis acid catalysts may be employed.
Aluminum chloride catalyst
The aluminum chloride catalyst may be fluorinated. The aluminum fluoride may be obtained by reacting aluminum chloride with a fluorinating agent.
Chromium oxide catalyst
The chromium oxide catalyst is preferably 1.5 < m < 3, more preferably 2 < m < 2.75, and even more preferably 2 < m < 2.3 when chromium oxide is labeled with CrOm. In use CrO m ·nH 2 When the chromium oxide is marked with O, the value of n is preferably 3 or less, more preferably 1 to 1.5.
The fluorinated chromia catalyst is preferably prepared by fluorination of a chromia catalyst. The fluorination is preferably carried out using HF, fluorocarbon, or the like. The fluorinated chromium oxide catalyst can be synthesized, for example, according to the method described in JP-A-05-146680.
Alumina catalyst
The alumina catalyst is preferably alpha-alumina, activated alumina, or the like. The activated alumina is preferably ρ -alumina, χ -alumina, κ -alumina, η -alumina, pseudo γ -alumina, σ -alumina, θ -alumina, or the like. In addition, a composite oxide containing alumina and other compounds may be used.
The composite oxide is preferably a silica alumina catalyst. Silica alumina catalystIs a silicon dioxide (SiO) 2 ) And alumina (Al) 2 O 3 ) When the total amount of silica and alumina is 100% by mass, the content of silica is preferably 20% by mass to 90% by mass, and more preferably 50% by mass to 80% by mass.
Alumina catalysts and silica alumina catalysts exhibit greater activity by fluorination. Before the alumina catalyst is used for the catalytic reaction, it is preferable to use the catalyst after fluorination in advance to prepare a fluorinated alumina catalyst. The silica alumina catalyst is preferably fluorinated in advance before being used in the catalyst reaction, and is used after being prepared into a fluorinated silica alumina catalyst.
The fluorinating agent for fluorinating the alumina catalyst and the silica alumina catalyst preferably uses F 2 Inorganic fluorinating agents such as HF, organic fluorinating agents of fluorocarbon system such as hexafluoropropylene, etc.
The method of fluorinating the alumina catalyst and the silica alumina catalyst is preferably a method of fluorinating the alumina catalyst by circulating a fluorinating agent under atmospheric pressure at a temperature of about 400 ℃ at room temperature (25 ℃).
Zeolite catalyst
Zeolite catalysts are widely used as zeolite of known type. The zeolite catalyst is preferably a crystalline aqueous aluminosilicate of an alkali or alkaline earth metal. The zeolite is preferably in form of A, X, LSX, etc. The alkali metal or alkaline earth metal in the zeolite is preferably potassium, sodium, calcium, lithium, or the like.
Zeolite catalysts exhibit greater activity by fluorination. Before the zeolite catalyst is used for the catalyst reaction, it is preferable to use the zeolite catalyst after the zeolite catalyst is prepared by fluorination in advance.
The fluorinating agent used for fluorinating the zeolite catalyst is preferably F 2 Inorganic fluorinating agents such as HF, organic fluorinating agents of fluorocarbon system such as hexafluoropropylene, etc.
The zeolite catalyst is preferably fluorinated by circulating a fluorinating agent at room temperature (25 ℃) and 400℃under atmospheric pressure.
Titanium oxide catalyst
The titanium oxide catalyst preferably contains titanium dioxide as a main component, and may contain one or more of various nonvolatile substances such as other metal oxides, hydroxides, sulfates, nitrates, phosphates, sulfides, and the like. The titanium oxide catalyst preferably contains 70 mass% or more of titanium dioxide.
The titanium dioxide is preferably anatase titanium dioxide, and the specific surface area is preferably 5m 2 /g～100m 2 Preferably, the pore volume is 0.2mL/g to 0.4mL/g. The shape of the catalyst is preferably shaped to form spheres. For example, CS-200, CS-300, CS-950, etc. are commercially available products.
As the catalyst, a fluorinated titanium oxide catalyst is preferably used from the viewpoint of high activity of the isomerization reaction, greater conversion of the reaction, and easy reduction of catalyst deterioration, and easy suppression of catalyst deterioration even when the isomerization reaction is carried out for a long period of time.
Titanium oxide catalyst
The iron oxide catalyst is preferably an iron catalyst such as iron oxide, iron oxyfluoride, or iron fluoride.
The above catalysts may be used alone or in combination of 2 or more.
Fluorination of catalysts
In the isomerization step of the present invention, a fluorinated metal oxide catalyst is preferably used as the catalyst. The catalyst exhibits a strong activity by fluorination of the catalyst, and deterioration of the catalyst is easily reduced, and by adjusting the pore volume, deterioration of the catalyst can be suppressed even if the isomerization reaction is performed for a long period of time.
The method of fluorinating the metal oxide catalyst preferably reacts the metal oxide with a fluorinating agent. Specifically, the metal oxide is fluorinated by circulating a fluorinating agent. The metal oxide in this case is a metal oxide constituting the fluorinated metal oxide.
The fluorinating agent is preferably a hydrofluorocarbon (R23: trifluoromethane, R32: difluoromethane, R41: monofluoromethane), a hydrochlorofluorocarbon (R22: chlorodifluoromethane, R21: dichloromonofluoromethane), a chlorofluorocarbon (R13: chlorotrifluoromethane, R11: trichloromonofluoromethane) or the like. The pore volume of the fluorinated metal oxide catalyst tends to be larger than that of hydrogen fluoride, and deterioration of the catalyst is easily reduced, and when the isomerization reaction described above is performed for a long period of time, deterioration of the catalyst is easily suppressed. The fluorinating agent may be used alone, or 2 or more kinds may be used in combination.
The fluorination conditions are not particularly limited, and the temperature is preferably 50 to 600 ℃, more preferably 100 to 500 ℃, from the viewpoint of easily reducing the deterioration of the catalyst and easily suppressing the deterioration of the catalyst even when the isomerization reaction is performed for a long period of time.
For the same reason, the pressure is preferably 0kPa to 1,000kPa, more preferably 0.1kPa to 500kPa.
For the same reason, the time for the fluorination is preferably 0.1 to 24 hours, more preferably 1 to 12 hours.
Examples of use of the catalyst
In the step of the isomerization reaction of the present invention, a fluorinated or nonfluorinated chromia catalyst, a fluorinated or nonfluorinated alumina catalyst, or the like is preferably used as the catalyst from the viewpoints of conversion, selectivity, and yield.
When a fluorinated or non-fluorinated lewis acid catalyst is used, the catalyst is preferably supported on a carrier. The support is preferably carbon, alumina (Al 2 O 3 ) Zirconium oxide (ZrO) 2 ) Silicon dioxide (SiO) 2 ) Titanium dioxide (TiO) 2 ) Etc. As the carbon, activated carbon, amorphous carbon, graphite, diamond, or the like is used.
In the step of isomerization, when the raw material compound is subjected to isomerization in the presence of a catalyst, the catalyst is preferably brought into contact with the raw material compound in a solid state (solid phase). The catalyst may be in the form of a powder, preferably in the form of pellets in a gas phase continuous flow reaction.
The specific surface area of the catalyst measured by the BET method (hereinafter, also referred to as "BET specific surface area") is preferably usually 10m 2 /g～3,000m 2 Preferably 10m 2 /g～2,500m 2 Preferably 20m 2 /g～2,000m 2 Per g, particularly preferably 30m 2 /g～1,500m 2 And/g. When the BET specific surface area of the catalyst is in the above range, the density of the catalyst particles is not excessively small, and therefore the isomerization reaction can be efficiently performed, and the target compound can be obtained with high conversion, yield and/or high selectivity.
Reaction temperature of isomerization reaction
In the step of the isomerization reaction of the present invention, the lower limit of the reaction temperature is preferably 10 ℃ or higher, more preferably 20 ℃ or higher, and still more preferably 30 ℃ or higher, from the viewpoint that the isomerization reaction can be performed more efficiently from the starting compound, the conversion is further improved, and the target compound can be obtained with a higher selectivity.
In the step of the isomerization reaction, the upper limit of the isomerization reaction is preferably 200 ℃ or less, more preferably 150 ℃ or less, and even more preferably 100 ℃ or less, from the viewpoint that the isomerization reaction can be performed more efficiently, the conversion is further improved, and the target compound is obtained at a higher selectivity, and from the viewpoint that the reduction in selectivity due to the decomposition or polymerization of the reaction product is further suppressed.
The isomerization step is preferably carried out at a reaction temperature of about room temperature (25 ℃).
Reaction time of isomerization reaction
In the step of the isomerization reaction of the present invention, the reaction time of the isomerization reaction is, for example, in the case of using a gas phase flow type, particularly high in conversion rate of the isomerization reaction, and from the viewpoint of obtaining the target compound in a higher yield and high selectivity, the contact time (W/F) of the raw material compound with the catalyst is [ W: weight of metal catalyst (g), F: the flow rate (cc/sec) ] of the raw material compound is preferably 1 g/sec/cc to 120 g/sec/cc, more preferably 5 g/sec/cc to 60 g/sec/cc, still more preferably 10 g/sec/cc to 50 g/sec/cc. The W/F is a parameter for setting the reaction time when the gas-phase flow-through reaction is used.
In the case of using a batch reaction, the contact time may be appropriately set.
The above-mentioned contact time means a time for which the raw material compound (substrate) and the catalyst are contacted.
Reaction pressure of isomerization reaction
In the step of the isomerization reaction of the present invention, the reaction pressure of the isomerization reaction is preferably from-0.05 MPa to 2MPa, more preferably from-0.01 MPa to 1MPa, and even more preferably from normal pressure to 0.5MPa, from the viewpoint of more efficient isomerization reaction.
In the present invention, when the pressure is not specifically described, the pressure is gauge pressure.
Reaction vessel for isomerization reaction
In the isomerization step of the present invention, the shape and structure of the reactor into which the raw material compound and the catalyst are charged and which causes the isomerization reaction are not particularly limited as long as the reactor can withstand the above temperature and pressure. The reactor for the isomerization reaction is preferably a vertical reactor, a horizontal reactor, a multitubular reactor or the like. The material of the reactor for the isomerization reaction is preferably glass, stainless steel, iron, nickel, iron-nickel alloy or the like.
Gas phase reaction
The isomerization step of the present invention can be preferably carried out by a gas phase reaction using either a flow-through type or a batch type in which a raw material compound (substrate) is continuously fed into a reactor and a target compound is continuously withdrawn from the reactor.
When the target compound remains in the reactor, the progress of the isomerization reaction is suppressed, and thus the flow-through type is preferable.
Continuous flow in the gas phase
The isomerization reaction process of the present invention is preferably carried out in the vapor phase, more preferably in the vapor phase continuous flow using a fixed bed reactor. When it is carried out in a gas-phase continuous flow, the apparatus, operation, etc. can be simplified and economically advantageous.
In the step of the isomerization reaction, the atmosphere in which the isomerization reaction is performed is preferably an inert gas atmosphere, a hydrogen fluoride gas atmosphere, or the like, from the viewpoint of suppressing deterioration of the catalyst. The inert gas is preferably nitrogen, helium, argon, or the like. From the viewpoint of cost reduction, nitrogen is preferably used as the inert gas. The concentration of the inert gas is preferably 0 to 50 mol% of the gas component introduced into the reactor.
The isomerization step can obtain the target compound with higher selectivity by appropriately adjusting the reaction temperature and the reaction time (contact time) by matching the catalyst.
(3) Target compound
The target compound of the present invention is an olefin having 4 or more carbon atoms and a double bond at the 2-position (isomerized olefin).
In the step of isomerization reaction, an olefin of a raw material compound is reacted, and the CC double bond thereof is shifted to the adjacent 2-position, thereby producing an olefin having a double bond at the 2-position.
The olefin of the target compound is preferably a perfluoroolefin. The perfluoroolefin is an olefin having a perfluoroalkyl group in which all hydrogen atoms are replaced with fluorine atoms.
The olefin of the target compound preferably has a perfluoroalkyl group having 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, still more preferably 1 to 6 carbon atoms, particularly preferably 1 to 4 carbon atoms, and most preferably 1 to 3 carbon atoms.
The perfluoroalkyl group is preferably a linear or branched perfluoroalkyl group. The perfluoroalkyl group is preferably trifluoromethyl (CF) 3 (-) and pentafluoroethyl (C) 2 F 5 －)。
Efficient isomerization from olefins, preferably 1,2,3, 4-octafluoro-1-butene, which are capable of starting compounds, and producing target compounds with high conversion, yield and/or high selectivityIn terms of the olefin, the olefin of the target compound is preferably a compound (C) having 4 carbon atoms 4 Compound) to a compound (C) having 8 carbon atoms 8 Compounds), more preferably C 4 A compound.
The olefin of the target compound is preferably 1,2,3, 4-octafluoro-2-butene.
The olefins of the target compound may be used alone, or 2 or more kinds may be used in combination. Commercially available olefins may also be used.
Preferred isomerisation reactions
The isomerization step of the present invention preferably isomerizes 1,2,3, 4-octafluoro-1-butene which is an olefin as a raw material compound, 1,2,3, 4-octafluoro-2-butene is produced as an olefin of the target compound.
After completion of the isomerization reaction, the target compound can be obtained by purifying the compound according to a usual method, if necessary.
(4) Compositions containing olefins
Preferably, the composition of the present invention comprises:
1,2,3, 4-octafluoro-2-butene (CF) 3 －CF＝CF－CF 3 )；
1,2,3, 4-octafluoro-1-butene (CF) 2 ＝CF－CF 2 －CF 3 ) The method comprises the steps of carrying out a first treatment on the surface of the And
octafluorocyclobutane (C-C) 4 F 8 )。
The composition is preferably used as an etching gas, a refrigerant, a heat transfer medium, a deposition gas, a block for organic synthesis, or a cleaning gas.
In the process of the present invention, an olefin having 4 or more carbon atoms and a double bond at the 2-position can be obtained as an isomerized olefin in the step of isomerization. It is also possible to obtain a composition containing an olefin having 4 or more carbon atoms and having a double bond at the 2-position of the target compound and an olefin having 4 or more carbon atoms and having a double bond at the 1-position of the starting compound.
The content of 1,2,3, 4-octafluoro-2-butene in the composition is preferably 80mol% or more and 99.9mol% or less, more preferably 90mol% or more and 99.9mol% or less, still more preferably 95mol% or more and 99.9mol% or less, particularly preferably 99mol% or more and 99.9mol% or less, based on 100mol% of the total amount of the composition.
Regarding the composition, the content of 1,2,3, 4-octafluoro-2-butene is preferably 80mol% or more, when the total amount of the composition is set to 100mol%, the content of 1,2,3, 4-octafluoro-1-butene and octafluorocyclobutane is preferably 20mol% or less.
The production method of the present invention can obtain 1,2,3, 4-octafluoro-2-butene with high selectivity, as a result, the content of components other than 1,2,3, 4-octafluoro-2-butene in the composition can be reduced. Therefore, the production method of the present invention can efficiently purify 1,2,3, 4-octafluoro-2-butene.
The composition is preferably used as an etching gas, a refrigerant, a heat transfer medium, or the like for forming a microstructure of the forefront of a semiconductor, a liquid crystal, or the like. The olefin-containing composition is preferably effectively usable for various applications such as deposition gas, block for organic synthesis, and cleaning gas.
The deposition gas is a gas that deposits an etch resistant polymer layer.
The block for organic synthesis means a substance capable of being made into a precursor of a compound having a highly reactive skeleton. Contacting a composition comprising 1,2,3, 4-octafluoro-2-butene with CF 3 Si(CH 3 ) 3 CF can be introduced in the reaction of the fluorine-containing organosilicon compound 3 Fluoroalkyl groups such as a radical, and the like, into a substance that can be made into a cleaning agent or a fluorine-containing pharmaceutical intermediate.
The embodiments of the present invention have been described above.
The form and details of the embodiments of the present invention may be variously modified without departing from the gist and scope of the claimed scope of the present invention.
Examples
Hereinafter, the present invention will be specifically described with reference to examples.
The present invention is not limited to these examples.
Examples
Raw material compound: 1,2,3, 4-octafluoro-1-butene (CF) 2 ＝CF－CF 2 －CF 3 )；
A target compound: 1,2,3, 4-octafluoro-2-butene (CF) 3 －CF＝CF－CF 3 )；
Gas chromatography: the product name "GC-2014" manufactured by Shimadzu corporation;
and (3) NMR: JEOL corporation, product name "400YH".
(1) Isomerization reactions using batch reactions
After adding a catalyst to a metal reaction vessel and covering the vessel with a lid to form a closed system, 1,2,3, 4-octafluoro-1-butene (raw material compound) was added. Thereafter, the mixture was stirred at 25℃at room temperature to initiate the isomerization reaction. Sampling at proper time, and taking the reaction system with unchanged composition as the end of fluorination.
Then, mass spectrometry was performed by gas chromatography/mass spectrometry (GC/MS) using gas chromatography, and structural analysis was performed by NMR using NMR spectrum. By mass spectrometry and structural analysis, it was confirmed that 1,2,3, 4-octafluoro-2-butene was produced as the target compound.
Table 1: example 1 batch reaction (catalyst fluorinated)
Alumina as a catalyst was added to the metal reaction vessel, and after the reaction vessel was covered with a lid to form a closed system, R22 (chlorodifluoromethane) as a fluorinating agent was added thereto, followed by stirring at room temperature to fluorinate the catalyst.
After the completion of the reaction, it was confirmed that 1,2,3, 4-octafluoro-2-butene was produced as the target compound from the results of mass spectrometry and structural analysis.
In the isomerization reaction, octafluorocyclobutane (C-C) is produced 4 F 8 、C318)。
Table 1: examples 2 to 12 batch reactions (catalyst not fluorinated)
Adding aluminum oxide, titanium oxide and Fe as catalysts into a metal reaction vessel 2 O 3 After a closed system is formed by covering silica alumina, zeolite, chromium oxide or aluminum chloride, 1,2,3, 4-octafluoro-1-butene is added.
After the completion of the reaction, it was confirmed that 1,2,3, 4-octafluoro-2-butene was produced as the target compound from the results of mass spectrometry and structural analysis.
In the isomerization reaction, octafluorocyclobutane (C-C) is produced 4 F 8 、C318)。
The results of each example are shown in table 1 below.
According to the results of the examples (Table 1), 1,2,3, 4-octafluoro-1-butene was subjected to an isomerization reaction in the presence of a Lewis acid catalyst, 1,2,3, 4-octafluoro-2-butene can be produced as a target compound with high conversion, yield and/or high selectivity.
TABLE 1
(2) Isomerization reactions using gas phase flow-through reactions
In the case of the gas-phase flow-through reaction, the contact time (W/F) between 1,2,3, 4-octafluoro-1-butene (raw material compound) and the Lewis acid catalyst is set at normal pressure 0 ) The raw material compound was allowed to flow through the reactor so as to be 11 g/sec/cc (%), 22 g/sec/cc (%) or 44 g/sec/cc (%).
The reaction is carried out in a gas phase continuous flow.
The reactor was heated to 100℃at 25℃to initiate the isomerisation reaction.
After the reaction had started, the fractions passing through the pest elimination column were collected after 1 hour.
Then, mass spectrometry was performed by gas chromatography/mass spectrometry (GC/MS) using gas chromatography, and structural analysis was performed by NMR using NMR spectrum. By mass spectrometry and structural analysis, it was confirmed that 1,2,3, 4-octafluoro-2-butene was produced as the target compound.
Table 2: examples 1 to 18, gas phase reactions (fluorination of catalyst)
After a catalyst was added to SUS tubing as a reaction tube and dried under a nitrogen atmosphere, the pressure was set to normal pressure, and the temperature was raised to 300 ℃. After the temperature was constant at 300 ℃, R22 (chlorodifluoromethane) of the fluorinating agent was circulated for 1 hour. Thereafter, the temperature was lowered to 25 ℃ (room temperature) and the isomerization reaction was started. After reaching 25℃at room temperature, 1,2,3, 4-octafluoro-1-butene was circulated so that the W/F became 44 g.sec/cc.
After the completion of the reaction, it was confirmed that 1,2,3, 4-octafluoro-2-butene was produced as the target compound from the results of mass spectrometry and structural analysis.
In the isomerization reaction, octafluorocyclobutane (C-C) is produced 4 F 8 、C318)。
Table 2: examples 19 to 21, gas phase reactions (catalyst not fluorinated)
Catalyst was added to SUS tubing as a reaction tube. After drying under a nitrogen atmosphere, 1,2,3, 4-octafluoro-1-butene was circulated at room temperature so that the pressure was set to normal pressure and the W/F was set to 44g sec/cc. The reactor was heated to 100℃at 25℃to initiate the isomerisation reaction.
After the completion of the reaction, it was confirmed that 1,2,3, 4-octafluoro-2-butene was produced as the target compound from the results of mass spectrometry and structural analysis.
In the isomerization reaction, octafluorocyclobutane (C-C) is produced 4 F 8 、C318)。
The results of each example are shown in table 2 below.
In Table 2, the contact time (W/F) means the degree of speed at which the raw material gas circulated flows, i.e., the time during which the catalyst and the raw material gas are contacted.
According to the results of the examples (Table 2), 1,2,3, 4-octafluoro-1-butene was subjected to an isomerization reaction in the presence of a Lewis acid catalyst, 1,2,3, 4-octafluoro-2-butene can be produced as a target compound with high conversion, yield and/or high selectivity.
TABLE 2
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Claims (5)

1. A process for producing an olefin having 4 or more carbon atoms and a double bond at the 2-position, characterized by comprising:
the method comprises a step of isomerizing an olefin having 4 or more carbon atoms and a double bond at the 1-position in the presence of a Lewis acid catalyst.
2. The method of manufacturing as claimed in claim 1, wherein:
which is 1,2,3, 4-octafluoro-2-butene (CF) 3 －CF＝CF－CF 3 ) Is characterized in that the manufacturing method of the glass fiber reinforced plastic material,
the production method comprises reacting 1,2,3, 4-octafluoro-1-butene (CF) 2 ＝CF－CF 2 －CF 3 ) And a step of carrying out an isomerization reaction in the presence of a Lewis acid catalyst.
3. The manufacturing method according to claim 1 or 2, characterized in that:
and (3) carrying out the isomerization reaction in a gas phase.
4. A composition comprising:
1,2,3, 4-octafluoro-2-butene (CF) 3 －CF＝CF－CF 3 )；
1,2,3, 4-octafluoro-1-butene(CF 2 ＝CF－CF 2 －CF 3 ) The method comprises the steps of carrying out a first treatment on the surface of the And
octafluorocyclobutane (C-C) 4 F 8 )。
5. The composition of claim 4, wherein:
as etching gas, refrigerant, heat transfer medium, deposition gas, block for organic synthesis, or cleaning gas.
CN202280047528.7A 2021-07-15 2022-07-12 Process for producing olefin Pending CN117597322A (en)

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JPS6052132B2 (en) * 1979-03-31 1985-11-18 ダイキン工業株式会社 Method for producing perfluoro-2-butene
JPS55133321A (en) * 1979-04-02 1980-10-17 Daikin Ind Ltd Preparation of perfluoro-2-butene
US4684760A (en) * 1986-02-24 1987-08-04 Phillips Petroleum Company Catalyst compositions useful for olefin isomerization and disproportionation
US4749819A (en) * 1987-03-27 1988-06-07 Shell Oil Company Terminal to interior double bond isomerization process for an olefinic molecule
US5177281A (en) * 1991-12-27 1993-01-05 Mobil Oil Corporation Double bond isomerization of 1-olefin containing feeds using ZSM-22, ZSM-23 or ZSM-35
US5304695A (en) * 1993-02-22 1994-04-19 Mobil Oil Corporation Double bond isomerization of olefin-containing feeds with minimal oligomerization using permanently surface acidity deactivated zeolite catalysts
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