CN117642373A - Process for producing olefin - Google Patents

Process for producing olefin Download PDF

Info

Publication number
CN117642373A
CN117642373A CN202280049957.8A CN202280049957A CN117642373A CN 117642373 A CN117642373 A CN 117642373A CN 202280049957 A CN202280049957 A CN 202280049957A CN 117642373 A CN117642373 A CN 117642373A
Authority
CN
China
Prior art keywords
olefin
hydrogenation
cfh
gas
general formula
Prior art date
Legal status (The legal status 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 status listed.)
Pending
Application number
CN202280049957.8A
Other languages
Chinese (zh)
Inventor
江藤友亮
中村新吾
松永隆行
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Daikin Industries Ltd
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 CN117642373A publication Critical patent/CN117642373A/en
Pending legal-status Critical Current

Links

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
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/44—Palladium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B61/00—Other general methods
    • 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
    • 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
    • C07C19/00—Acyclic saturated compounds containing halogen atoms
    • C07C19/08—Acyclic saturated compounds containing halogen atoms containing fluorine
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K13/00—Etching, surface-brightening or pickling compositions
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C09K5/02—Materials undergoing a change of physical state when used
    • C09K5/04—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa

Landscapes

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

Abstract

The technical problems to be solved by the invention are as follows: the hydrogenated olefins are produced by hydrogen substitution. The method for producing an olefin comprises a step of causing a hydrogenation reaction in the presence of an activated carbon catalyst carrying a noble metal or rare metal.

Description

Process for producing olefin
Technical Field
The present invention relates to a process for producing an olefin.
Background
Patent document 1 discloses a method for producing trifluoroethylene, which includes a step of bringing chlorotrifluoroethylene into contact with hydrogen in the presence of a catalyst composed of palladium or platinum supported on activated carbon.
Prior art literature
Patent literature
Patent document 1: japanese patent application laid-open No. 2013-534529
Disclosure of Invention
Technical problem to be solved by the invention
The invention aims to solve the technical problems that: the hydrogenated olefins are produced by hydrogen substitution.
Technical scheme for solving technical problems
The invention comprises the following technical proposal.
A process for producing an olefin represented by the general formula (1) below, which comprises a step of subjecting an olefin represented by the general formula (2) below to a hydrogenation reaction in the presence of an activated carbon catalyst supporting a noble metal or rare metal.
(wherein R is 1 、R 2 And R is 3 The same or different, represent fluorine or perfluoroalkyl. )
(wherein X is a halogen atom, R 1 、R 2 And R is 3 The same or different, represent fluorine or perfluoroalkyl. Wherein, when X is a chlorine atom, R 1 、R 2 And R is 3 Any one or more of them represents a perfluoroalkyl group. )
The production method according to item 1, wherein the hydrogenation reaction is carried out in a gas phase.
Item 3. The production method according to item 1 or 2 above, wherein the noble metal or rare metal is at least 1 noble metal or rare metal selected from palladium (Pd), platinum (Pt), rhodium (Rh), ruthenium (Ru) and manganese (Mn).
Item 4. A composition comprising:
CF 3 －CF＝CH－CF 3 ；
CF 3 －CFH－CFH－CF 3 the method comprises the steps of carrying out a first treatment on the surface of the And
CF 3 －CFH－CFH－CF 2 H。
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 using the present invention, a hydrogenated olefin can be efficiently produced by hydrogen substitution.
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.
The inventors of the present invention have made intensive studies and as a result, have found that by performing a step of hydrogenating an olefin as a raw material compound in the presence of a palladium-supported activated carbon catalyst, the hydrogenation reaction can be efficiently performed, and that a hydrogenated olefin can be produced with a high conversion (yield) and a high selectivity.
The present invention has been completed based on these findings and further repeated studies.
The present invention includes the following embodiments.
The process for producing an olefin represented by the general formula (1) of the present invention comprises a step of subjecting an olefin represented by the general formula (2) to hydrogenation in the presence of an activated carbon catalyst supporting a noble metal or rare metal.
(wherein R is 1 、R 2 And R is 3 The same or different, represent fluorine or perfluoroalkyl. )
(wherein X is a halogen atom, R 1 、R 2 And R is 3 The same or different, represent fluorine or perfluoroalkyl. Wherein, when X is a chlorine atom, R 1 、R 2 And R is 3 Any one or more of them represents a perfluoroalkyl group. )
The production method of the present invention preferably includes the step of performing the hydrogenation reaction in a gas phase.
The production method of the present invention preferably uses at least 1 noble metal or rare metal selected from the group consisting of palladium (Pd), platinum (Pt), rhodium (Rh), ruthenium (Ru) and manganese (Mn).
The composition of the present invention comprises:
CF 3 －CF＝CH－CF 3 ；
CF 3 －CFH－CFH－CF 3 the method comprises the steps of carrying out a first treatment on the surface of the And
CF 3 －CFH－CFH－CF 2 H。
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 satisfies the above conditions, whereby the hydrogenation reaction can be efficiently performed, and the hydrogenated olefin can be produced with a high conversion (yield) and a high selectivity.
In the present invention, the "conversion" means a ratio (mol%) of the total molar amount of compounds (hydrogenated olefin, etc.) other than the raw material compounds contained in the gas flowing out from the outlet of the reactor to the molar amount of the raw material compounds (halogen atom-containing olefin) supplied into the reactor.
In the present invention, the term "selectivity" means a ratio (mol%) of the total molar amount of the target compounds (hydrogenated olefins, etc.) contained in the gas flowing out from the outlet of the reactor to the total molar amount of the compounds (hydrogenated olefins, etc.) other than the raw material compounds in the effluent gas.
The process for producing an olefin of the present invention can efficiently hydrogenate an olefin containing a halogen atom as a raw material compound, and can produce a hydrogenated olefin with a high conversion (yield) and a high selectivity.
(1) Raw material compound
The starting compound of the present invention is an olefin represented by the general formula (2).
(wherein X is a halogen atom, R 1 、R 2 And R is 3 The same or different, represent fluorine or perfluoroalkyl. Wherein, when X is a chlorine atom, R 1 、R 2 And R is 3 Any one or more of them represents a perfluoroalkyl group. )
In the formula (2) of the olefin, X is a halogen atom, R 1 、R 2 And R is 3 The same or different, represent fluorine or perfluoroalkyl.
In the formula (2) of the olefin, when X is a chlorine atom, R 1 、R 2 And R is 3 Any one or more of them represents a perfluoroalkyl group.
The halogen atom is preferably a fluorine atom, a bromine atom, an iodine atom or a chlorine atom.
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 olefin represented by the general formula (2) of the raw material compound preferably has 2 to 8 carbon atoms, more preferably 2 to 4 carbon atoms, even more preferably 4 carbon atoms, from the viewpoint that the hydrogenation reaction can be efficiently carried out in the presence of the activated carbon catalyst supporting a noble metal or rare metal and the hydrogenated olefin can be produced at a high conversion, yield and/or high selectivity.
R of olefin represented by general formula (2) of raw material compound 1 、R 2 And R is 3 The same or different, represent fluorine or perfluoroalkyl.
The olefin of the formula (2) of the starting compound is preferably perfluoro-2-butene (F) 3 C－CF＝CF－CF 3 ) Perfluoro-1-butene (CF) 3 －CF 2 －CF＝CF 2 ) Etc.
The olefins represented by the general formula (2) of the raw material compound may be used alone or in combination of 2 or more kinds. Commercially available olefins may also be used.
(2) Hydrogenation reaction
In the hydrogenation step of the present invention, an olefin represented by the general formula (2) is hydrogenated using palladium-supported activated carbon as a catalyst.
In the hydrogenation step, the olefin represented by the general formula (2) as the starting compound preferably has 2 to 8 carbon atoms, more preferably 2 to 4 carbon atoms, and even more preferably 4 carbon atoms, from the viewpoint that the hydrogenated olefin can be produced at a high conversion, yield and/or high selectivity.
In the hydrogenation step, the raw material compound is represented by the general formula (2) in terms of being capable of efficiently subjecting an olefin to hydrogenation in the presence of a palladium-supported activated carbon catalyst to produce a hydrogenated olefin at a high conversion, yield and/or high selectivityThe olefins shown are preferably R 1 、R 2 And R is 3 The same or different, represent fluorine or perfluoroalkyl.
The olefin of the formula (2) of the starting compound is preferably perfluoro-2-butene (CF) 3 －CF＝CF－CF 3 ) The olefin of the general formula (1) of the target compound to be hydrogenated is preferably 1,2, 4-heptafluoro-2-butene (CF) 3 －CF＝CH－CF 3 )((Z/E)－1327myz))。
Noble or rare metal-supported activated carbon catalyst
(noble Metal or rare Metal catalyst carried by activated carbon)
The hydrogenation step of the present invention is to hydrogenate an olefin represented by the general formula (2) of a raw material compound using an activated carbon catalyst supporting a noble metal or rare metal as a catalyst to produce a hydrogenated olefin represented by the general formula (1), preferably 1,2, 4-heptafluoro-2-butene, of a target compound.
The hydrogenation reaction is preferably carried out in the gas phase.
As the hydrogenation catalyst, the noble metal or rare metal is preferably at least 1 noble metal or rare metal selected from palladium (Pd), platinum (Pt), rhodium (Rh), ruthenium (Ru), and manganese (Mn).
More preferably, the hydrogenation catalyst is one in which the noble metal or rare metal is palladium (Pd) and the carrier is activated carbon, and the use of the palladium-supported activated carbon catalyst can provide a high metal surface area and thus a high hydrogenation reaction rate.
The particle diameter of the activated carbon support is preferably about 0.1mm to 100 mm.
The palladium loading is preferably about 0.01 to 20 mass%, more preferably about 0.1 to 10 mass% based on the total mass of the catalyst used in the hydrogenation step.
The method for preparing the catalyst can be widely known. For example, a catalyst in which palladium metal is supported on an activated carbon support can be obtained by immersing the activated carbon support in a solution containing palladium metal, impregnating the support with the solution, and then, if necessary, neutralizing and firing the solution. In this case, the amount of the noble metal or rare metal supported on the carrier is adjusted according to the concentration of the solution, the impregnation time, and the like.
2 Hydrogen usage (H/olefin molar ratio)
In the hydrogenation step of the present invention, the amount of hydrogen to be used is preferably 0.1 to 10 moles (H 2 Molar ratio of olefin: 0.1 to 10), more preferably 1 to 5 moles (H) 2 Molar ratio of olefin: 1 to 5), more preferably 1 to 3 moles (H) 2 Molar ratio of olefin: 1 to 3), particularly preferably 1.1 mol (H) 2 Molar ratio of olefin: 1.1).
Reaction temperature of hydrogenation reaction
In the hydrogenation step of the present invention, the palladium-supported activated carbon catalyst is used, and the lower limit of the reaction temperature is preferably 100℃or higher, more preferably 150℃or higher, and even more preferably 200℃or higher, from the viewpoint that the hydrogenation reaction can be performed more efficiently, the conversion is further improved, and the target compound can be obtained from the raw material compound with a higher selectivity.
In the hydrogenation step, the upper limit of the hydrogenation is preferably 800 ℃ or less, more preferably 600 ℃ or less, still more preferably 500 ℃ or less, and particularly preferably 400 ℃ or less, from the viewpoint that the hydrogenation can be performed more efficiently, the conversion is further improved, and the target compound is obtained at a higher selectivity, and the reduction in selectivity due to the decomposition or polymerization of the reaction product is further suppressed.
Reaction time of hydrogenation reaction
In the hydrogenation step of the present invention, the reaction time of the hydrogenation is, for example, in the case of using a gas phase flow type, particularly high in conversion rate of the hydrogenation, and from the viewpoint of obtaining the target compound in a higher yield and high selectivity, the contact time (W/F) [ 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 3 g/sec/cc to 100 g/sec/cc, and still more preferably 5 g/sec/cc to 80 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 hydrogenation reaction
In the hydrogenation step of the present invention, the reaction pressure of the hydrogenation 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 hydrogenation.
In the present invention, when the pressure is not specifically described, the pressure is gauge pressure.
Reaction vessel for hydrogenation
In the hydrogenation step of the present invention, the shape and structure of the reactor into which the raw material compound and the catalyst are introduced and subjected to hydrogenation are not particularly limited as long as the reactor can withstand the above temperature and pressure. The reactor for the hydrogenation reaction is preferably a vertical reactor, a horizontal reactor, a multitubular reactor or the like. The material of the hydrogenation reactor is preferably glass, stainless steel, iron, nickel, iron-nickel alloy or the like.
Gas phase reaction
The hydrogenation step of the present invention is preferably carried out by a gas phase reaction, and can be carried out in 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 reaction is preferably performed in a flow-through manner because the reaction is suppressed from proceeding excessively.
Continuous flow in the gas phase
The hydrogenation reaction step of the present invention is preferably carried out in a gas phase, more preferably in a gas 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 hydrogenation step, the atmosphere in which the hydrogenation 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. Among the inert gases, nitrogen is preferably used from the viewpoint of cost reduction. The concentration of the inert gas is preferably 0 to 50 mol% of the gas component introduced into the reactor.
When the hydrogenation step is carried out in a gas phase in the presence of a catalyst, the target compound can be obtained with a higher selectivity by appropriately adjusting the reaction temperature and the reaction time (contact time) particularly by matching the catalyst.
(3) Target compound
The target compound of the present invention is an olefin (hydrogenated olefin) represented by the general formula (1).
(wherein R is 1 、R 2 And R is 3 The same or different, represent fluorine or perfluoroalkyl. )
In the hydrogenation step, the starting compound is represented by the general formula (2), and X (halogen atom) thereof is replaced with hydrogen to produce a hydrogen-substituted olefin.
In the formula (1) of the olefin, R 1 、R 2 And R is 3 The same or different, represent fluorine or perfluoroalkyl.
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 olefin represented by the general formula (1) of the target compound is preferably a compound having 2 carbon atoms (C) 2 Compounds) to C8 Compound (C) 8 Compounds), more preferably C 2 Compounds C 4 Compounds, more preferably C 4 A compound.
The olefin represented by the general formula (1) of the objective compound is preferably R in terms of being capable of efficiently subjecting the olefin (halogen atom) represented by the general formula (2) of the raw material compound to hydrogenation reaction in the presence of the palladium-supported activated carbon catalyst and producing the hydrogenated olefin at a high conversion, yield and/or high selectivity 1 、R 2 And R is 3 The same or different, represent fluorine or perfluoroalkyl.
The olefin represented by the general formula (1) of the target compound is preferably 1,2, 4-heptafluoro-2-butene.
The olefins represented by the general formula (1) of the raw material compound may be used alone or in combination of 2 or more kinds. Commercially available olefins may also be used.
Preferred hydrogenation reactions
In the hydrogenation step of the present invention, it is preferable to hydrogenate perfluoro-2-butene, which is an olefin of a raw material compound, to produce 1,2, 4-heptafluoro-2-butene, which is an olefin of a target compound, using a palladium-supported activated carbon catalyst.
After the hydrogenation reaction, the target compound can be obtained by purifying according to a usual method, if necessary.
(4) Containing olefinsIs a composition of (a)
Preferably, the composition of the present invention comprises:
CF 3 －CF＝CH－CF 3 (1, 2, 4-heptafluoro-2-butene);
CF 3 －CFH－CFH－CF 3 the method comprises the steps of carrying out a first treatment on the surface of the And
CF 3 －CFH－CFH－CF 2 H。
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.
By the production method of the present invention, an olefin represented by the general formula (1) can be obtained. The olefin represented by the general formula (1) of the target compound and the olefin represented by the general formula (2) of the raw material compound are also sometimes obtained as a composition.
CF contained in the composition 3 －CFH－CFH－CF 3 For example, an alkane compound derived from perfluoro-2-butene of the starting compound.
CF contained in the composition 3 －CFH－CFH－CF 2 H is, for example, an alkane compound of the 3H form.
The content of 1,2, 4-heptafluoro-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, and particularly preferably 99mol% or more and 99.9mol% or less, based on 100mol% of the total amount of the composition.
Regarding the composition, the total amount of the composition was taken as 100mol%, CF 3 －CF＝CH－CF 3 The content of CF is preferably 80mol% or more 3 －CFH－CFH－CF 3 And CF (compact F) 3 －CFH－CFH－CF 2 The content of H is preferably 20mol% or less.
By the production method of the present invention, 1,2, 4-heptafluoro-2-butene (hydrogenated olefin) can be obtained with a particularly high selectivity, as a result, the content of components other than 1,2, 4-heptafluoro-2-butene in the composition can be reduced. Therefore, the production method of the present invention can efficiently purify 1,2, 4-heptafluoro-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 forming a precursor of a compound having a skeleton with high reactivity. The composition containing 1,2, 4-heptafluoro-2-butene is reacted 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: perfluoro-2-butene (F) 3 C－CF＝CF－CF 3 )；
A target compound: 1,2, 4-heptafluoro-2-butene (F) 3 C－CF＝CH－CF 3 )
((Z/E)－1327myz))；
Gas chromatography: the product name "GC-2014" manufactured by Shimadzu corporation;
and (3) NMR: JEOL corporation, product name "400YH".
As the reaction tube, SUS piping (outer diameter: 1/2 inch) was used, and the palladium-supported activated carbon catalyst was filled. After drying at 200℃for 3 hours under nitrogen atmosphere, the temperature was raised to 400 ℃. After the temperature is raised to 400 ℃, the temperature is reduced to the reaction temperature, the hydrogen diluted by the nitrogen flows, the concentration of the hydrogen is slowly increased, and finally the hydrogenation treatment of the catalyst is carried out by using 100% hydrogen.
The gas-phase flow-through reaction was carried out under normal pressure so as to allow the perfluoro-2-butene (raw material compound) to contact the palladium-supported activated carbon catalyst (1% Pd/C) for a period of time (W/F) 0 ) The raw material compound was allowed to flow through the reactor so as to be 8 g/sec/cc (%), 17 g/sec/cc (%), 38 g/sec/cc (%), 60 g/sec/cc (%) or 78 g/sec/cc (%).
The hydrogen consumption is H 2 Molar ratio of olefin: 1.1.
(H 2 :1.1 moles, moles of olefin: 1 mole)
The reactor was heated at 200 ℃, 300 ℃ or 400 ℃ to initiate the hydrogenation of fluorine atoms. After the start of the hydrogenation, the fraction passing through the pest elimination column was 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.
After completion of the reaction, it was confirmed that 1,2, 4-heptafluoro-2-butene was produced as the target compound from the results of mass spectrometry and structural analysis.
Perfluoro-2-butene (F) derived from the starting compound was produced 3 C－FC＝CF－CF 3 ) An alkane compound of (a): CF (compact flash) 3 －CFH－CFH－CF 3 Paraffin compounds of 3H body: CF (compact flash) 3 －CFH－CFH－CF 2 H。
The results of each example are shown in table 1 below.
In Table 1, the contact time (W/F) means the rate at which the raw material gas to be circulated flows, i.e., the time for which the catalyst and the raw material gas are contacted.
According to the results of examples (table 1), when 1,2, 4-heptafluoro-2-butene, which is a target compound, was produced by adding hydrogen to perfluoro-2-butene, which is a raw material compound, in the presence of a palladium-supported activated carbon catalyst, and performing hydrogenation reaction, hydrogenation reaction was efficiently performed, and hydrogenated olefins were produced at high conversion, yield and/or high selectivity. The use of palladium supported activated carbon catalysts is a particularly preferred embodiment.
[ Table 1 ]

Claims (5)

1. A process for producing an olefin represented by the general formula (1), characterized by:
the production method comprises a step of subjecting an olefin represented by the general formula (2) to hydrogenation in the presence of an activated carbon catalyst supporting a noble metal or rare metal,
in the formula (1), R 1 、R 2 And R is 3 Identical or different, represent fluorine or perfluoroalkyl,
in the formula (2), X is a halogen atom, R 1 、R 2 And R is 3 Identical or different, represent fluorine or perfluoroalkyl groups, R being the case when X is a chlorine atom 1 、R 2 And R is 3 Any one or more of them represents a perfluoroalkyl group.
2. The method of manufacturing as claimed in claim 1, wherein:
and (3) carrying out the hydrogenation reaction in a gas phase.
3. The manufacturing method according to claim 1 or 2, characterized in that:
the noble metal or rare metal is at least 1 noble metal or rare metal selected from palladium (Pd), platinum (Pt), rhodium (Rh), ruthenium (Ru), and manganese (Mn).
4. A composition comprising:
CF 3 －CF＝CH－CF 3 ；
CF 3 －CFH－CFH－CF 3 the method comprises the steps of carrying out a first treatment on the surface of the And
CF 3 －CFH－CFH－CF 2 H。
5. the composition of claim 4, wherein:
as etching gas, refrigerant, heat transfer medium, deposition gas, block for organic synthesis, or cleaning gas.
CN202280049957.8A 2021-07-15 2022-07-12 Process for producing olefin Pending CN117642373A (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP2021117229A JP7348535B2 (en) 2021-07-15 2021-07-15 Alkene production method
JP2021-117229 2021-07-15
PCT/JP2022/027339 WO2023286752A1 (en) 2021-07-15 2022-07-12 Alkene production method

Publications (1)

Publication Number Publication Date
CN117642373A true CN117642373A (en) 2024-03-01

Family

ID=84919465

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202280049957.8A Pending CN117642373A (en) 2021-07-15 2022-07-12 Process for producing olefin

Country Status (5)

Country Link
JP (2) JP7348535B2 (en)
KR (1) KR20240032994A (en)
CN (1) CN117642373A (en)
TW (1) TW202313535A (en)
WO (1) WO2023286752A1 (en)

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2668769B1 (en) * 1990-11-06 1992-12-31 Atochem MANUFACTURE OF FLUOROETHYLENES AND CHLOROFLUOROETHYLENES.
JP3407379B2 (en) * 1993-06-10 2003-05-19 ダイキン工業株式会社 Method for producing 1,1,1,3,3-pentafluoropropane
US5562855A (en) * 1994-09-29 1996-10-08 E. I. Du Pont De Nemours And Company Octafluorobutane compositions
US8003003B2 (en) 2008-04-04 2011-08-23 Dow Global Technologies Llc Refrigerant composition
CN102026946B (en) 2008-07-18 2014-03-12 日本瑞翁株式会社 Method for producing hydrogen-containing fluoroolefin compound
US20130131402A1 (en) 2010-07-01 2013-05-23 Solvay Specialty Polymers Italy S.P.A. Process for the synthesis of trifluoroethylene
CN106029615B (en) 2014-02-20 2018-11-09 Ａｇｃ株式会社 The purification process of fluid containing trifluoro-ethylene and the manufacturing method of trifluoro-ethylene
JP6827246B2 (en) 2019-02-21 2021-02-10 ダイキン工業株式会社 Method for producing halogenated butene compound

Also Published As

Publication number Publication date
TW202313535A (en) 2023-04-01
JP7348535B2 (en) 2023-09-21
JP2023013217A (en) 2023-01-26
JP2023099721A (en) 2023-07-13
KR20240032994A (en) 2024-03-12
WO2023286752A1 (en) 2023-01-19

Similar Documents

Publication Publication Date Title
JP5477290B2 (en) Method for producing hydrogen-containing fluoroolefin compound
JP6673413B2 (en) Method for producing fluoroolefin
EP2209759B1 (en) Manufacture of 1,1,1,2,3,3-hexafluoropropane and 1,1,1,2-tetrafluoropropane via catalytic hydrogenation
CN106660908B (en) Process for producing hydrofluoroolefin
KR20090071510A (en) Process for the Manufacture of Fluorinated Olefins
CA2009188A1 (en) Hydrogenolysis/dehydrohalogenation process
JP5693571B2 (en) Method for producing pentafluoropropane
JP5784594B2 (en) Method for producing hexafluoropropane
JP7206501B2 (en) Method for producing halogenated cycloalkane compound
CN117642373A (en) Process for producing olefin
KR101639487B1 (en) Manufacturing apparatus of trans-1,4-cyclohexanedimethanol for simplifying process
KR101659171B1 (en) Method of direct conversion to trans-1,4-cyclohexanedimethanol
CN114746384B (en) Method for producing alkane compound
JP7553758B2 (en) Method for producing vinyl compounds
CN113329987B (en) Process for producing fluoroethane and process for producing fluoroolefin
JP7177156B2 (en) Continuous production method for 2,3-butanediol
JP3794859B2 (en) Method for producing perhalogenated cyclopentane
WO2020213600A1 (en) Method for producing 1-chloro-2,3,3,3-tetrafluoropropene
EP0632001B1 (en) Method for producing a hydrofluorocarbon
JP2023143030A (en) Method for producing 1,3-cyclopentanediol
JPH03284638A (en) Production of hydrogen-containing haloethane
JP2005539078A (en) Continuous process for optically pure (S) -β-hydroxy-γ-butyrolactone

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination