CN109689604A - The manufacturing method of the chloro- 2,3,3- trifluoro propene of 1- - Google Patents
The manufacturing method of the chloro- 2,3,3- trifluoro propene of 1- Download PDFInfo
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- CN109689604A CN109689604A CN201780055755.3A CN201780055755A CN109689604A CN 109689604 A CN109689604 A CN 109689604A CN 201780055755 A CN201780055755 A CN 201780055755A CN 109689604 A CN109689604 A CN 109689604A
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- 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
- C07C17/358—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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- 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
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B61/00—Other general methods
Abstract
The present invention, which provides, to make the E body of 1233yd and any manufacturing method to react of Z body with industrial advantageous and efficient method choice.Make the 1233yd (E) in the feedstock composition for containing 1233yd (E) and 1233yd (Z) with the molar ratio for the equilibrium ratio being different from a temperature of isomerization reaction that isomerization reaction occur to manufacture 1233yd (Z) or the 1233yd (Z) and isomerization reaction occurs to manufacture the manufacturing method of the 1233yd of 1233yd (E).
Description
Technical field
The present invention relates to the manufacturing methods of the chloro- 2,3,3- trifluoro propene of 1-.
Background technique
Hydrochlorofluorocarbons (HCFC) has a negative impact to ozone layer, therefore plan limits its production.HCFC for example including 3,
The chloro- 1,1,1,2,2- pentafluoropropane (HCFC-225ca) of 3- bis- and the chloro- 1,1,2,2,3- pentafluoropropane (HCFC- of 1,3- bis-
225cb) etc., with the limitation to HCFC, it is expected that developing the compound for substituting above-mentioned HCFC.
Substitute HCFC compound an example be 1- chloro- 2,3,3- trifluoro propenes (HCFO-1233yd, hereinafter referred to as
"1233yd").The chamber effect potential value (GWP) of 1233yd is low, is that can be used for cleaning agent, solvent, refrigerant, foaming agent gentle
The new compound of colloidal sol purposes.There are the E bodies of 1233yd and Z body by 1233yd as geometric isomer, depending on the application and to mixed
The intermiscibility etc. of synthesis point, be used alone the Z body of 1233yd or the E body of 1233yd, or uses the Z body and 1233yd of 1233yd
The mixture of E body.
As the manufacturing method of 1233yd, disclosing makes 3- chloro- 1,1,2,2- tetrafluoropropane by catalyst of chromium hydroxide
(HCFC-244ca) under stream of nitrogen gas under gas phase with hydrogen fluoride reaction to manufacture 1,1,2,2,3- pentafluoropropane (HCFC-
Method (see, for example patent document 1) 245ca).The 1233yd as by-product is generated in this method.Therefore, pass through recycling
The above-mentioned resulting composition of reaction can obtain 1233yd to separate the 1233yd contained in the composition.
But the 1233yd generated in the above method is the mixture of the E body of 1233yd and the Z body of 1233yd, it is not public
It opens the E body of 1233yd and the separation of Z body.In addition, the above method does not adjust the E body of 1233yd and the composition of Z body yet.
Therefore, for the reaction of any one of E body and the Z body that can selectively make 1233yd and with industrial advantageous and
Efficient mode manufactures the method for the 1233yd of composition requirement, and there are demands.
Existing technical literature
Patent document
Patent document 1: International Publication No. 1994/14737
Summary of the invention
The technical problems to be solved by the invention
The purpose of the present invention is to provide the E bodies that can make 1233yd with industrial advantageous and efficient method choice
Any with Z body reacts to manufacture the manufacturing method of the 1233yd of composition requirement.
Technical scheme applied to solve the technical problem
The present invention provides the manufacturing method of the 1233yd of following compositions.
[1] chloro- 2 1-, the manufacturing method of 3,3- trifluoro propenes (Z), wherein make to be different from defined isomerization reaction temperature
The molar ratio of equilibrium ratio (molar ratio) under degree contains the chloro- 2,3,3- trifluoro propene (E) of 1- and the chloro- 2,3,3- trifluoro propene of 1-
(Z) the chloro- 2,3,3- trifluoro propene (E) of the 1- in feedstock composition carries out isomerization at a temperature of the isomerization reaction
Reaction is to manufacture the chloro- 2,3,3- trifluoro propene (Z) of 1-.
[2] 1- chloro- 2 as described in [1], the manufacturing method of 3,3- trifluoro propenes (Z), wherein in the feedstock composition,
Molar ratio (the chloro- 2,3,3- tri- of 1- of the chloro- 2,3,3- trifluoro propene (Z) of 1- and the chloro- 2,3,3- trifluoro propene (E) of the 1-
The chloro- 2,3,3- trifluoro propene (E) of fluoropropene (Z)/1-) it is less than the equilibrium ratio (molar ratio) at a temperature of the isomerization reaction.
[3] 1- chloro- 2 as described in [1] or [2], the manufacturing method of 3,3- trifluoro propenes (Z), wherein the isomerization is anti-
It should be by carrying out the feedstock composition and metallic catalyst and contact.
[4] 1- chloro- 2 as described in [3], the manufacturing method of 3,3- trifluoro propenes (Z), wherein the metallic catalyst is
At least one kind of substance in metal simple-substance, alloy, metal oxide and metal halide.
[5] 1- chloro- 2 as described in [3] or [4], the manufacturing method of 3,3- trifluoro propenes (Z), wherein constitute the metal
The metal of catalyst is selected from group-4 metal element, the 6th race's metallic element, the 8th race's metallic element, the 9th race's metallic element, the
At least one kind of element in 10 race's metallic elements, the 11st race's metallic element, the 12nd race's metallic element and the 13rd race's metallic element.
[6] 1- chloro- 2 as described in any one of [3]~[5], the manufacturing method of 3,3- trifluoro propenes (Z), wherein described
Metallic catalyst is at least one kind of compound in metal oxide and metal halide.
[7] 1- chloro- 2 as described in any one of [4]~[6], the manufacturing method of 3,3- trifluoro propenes (Z), wherein described
Metal oxide is at least one kind of in aluminium oxide and chromium oxide.
[8] 1- chloro- 2 as described in any one of [4]~[6], the manufacturing method of 3,3- trifluoro propenes (Z), wherein described
Metal halide is compound obtained by a part of metal chloride is fluorinated.
[9] 1- chloro- 2 as described in any one of [1]~[8], the manufacturing method of 3,3- trifluoro propenes (Z), wherein described
Isomerization reaction temperature is at 0 DEG C or more 500 DEG C or less.
[10] 1- chloro- 2 as described in any one of [1]~[9], the manufacturing method of 3,3- trifluoro propenes (Z), wherein institute
Isomerization reaction is stated to carry out under liquid phase.
[11] 1- chloro- 2 as described in any one of [1]~[9], the manufacturing method of 3,3- trifluoro propenes (Z), wherein institute
Isomerization reaction is stated to carry out under gas phase.
[12] 1- chloro- 2 as described in [11], the manufacturing method of 3,3- trifluoro propenes (Z), which is characterized in that the isomery
Change reaction to carry out in the presence of inert gas.
[13] 1- chloro- 2 as described in any one of [11] or [12], the manufacturing method of 3,3- trifluoro propenes (Z), wherein
The isomerization reaction is carried out at 0 DEG C or more 260 DEG C or less.
[14] chloro- 2 1-, the manufacturing method of 3,3- trifluoro propenes (E), wherein make to be different from defined isomerization reaction
At a temperature of the molar ratio of equilibrium ratio (molar ratio) contain the chloro- 2,3,3- trifluoro propene (E) of 1- and the chloro- 2,3,3- trifluoro propene of 1-
(Z) the chloro- 2,3,3- trifluoro propene (Z) of the 1- in feedstock composition carries out isomerization at a temperature of the isomerization reaction
Reaction is to manufacture the chloro- 2,3,3- trifluoro propene (E) of 1-.
[15] 1- chloro- 2 as described in [14], the manufacturing method of 3,3- trifluoro propenes (E), wherein the feedstock composition
In, the 1- chloro- 2,3,3- trifluoro propenes (Z) and the 1- chloro- 2, the molar ratio (1- chloro- 2,3,3- of 3,3- trifluoro propenes (E)
The chloro- 2,3,3- trifluoro propene (E) of trifluoro propene (Z)/1-) it is greater than the equilibrium ratio (molar ratio) at a temperature of the isomerization reaction.
In the present specification, for halogenated hydrocarbon, the abbreviation of its compound is described in the bracket after compound name,
In the present specification as needed using its abbreviation to replace compound name.In addition, for intramolecular is with double bond and there are E
The compound of body and Z body marks (E), (Z) to be indicated at the end of E body and the abbreviation of the respective compound of Z body.In addition, changing
Close the end unmarked (E) of the abbreviation of name, (Z) then indicates E body and/or Z body.
Invention effect
The manufacturing method of the Z body of 1233yd through the invention, can be with industrially advantageous and efficient method choice
The E body of 1233yd is set to react to manufacture the Z body of 1233yd to property.
The manufacturing method of the E body of 1233yd through the invention, can be with industrially advantageous and efficient method choice
The Z body of 1233yd is set to react to manufacture the E body of 1233yd to property.
Detailed description of the invention
Fig. 1 be indicate the Z body of 1233yd under each isomerization reaction temperature relative to 1233yd E body and Z body it is total
There are the figures of ratio (mole %).
Specific embodiment
Embodiments of the present invention are described in detail below.
[manufacturing method of 1233yd (Z) or 1233yd (E)]
The manufacturing method of the 1233yd of one embodiment of the present invention is to prepare as shown in following formula [1] to be different from
The molar ratio of equilibrium ratio at a temperature of isomerization reaction contains 1- chloro- 2,3,3- trifluoro propenes (E) (HCFO-1233yd (E), with
Under be also denoted as " 1233yd (E) ") and 1- chloro- 2, (HCFO-1233yd (Z), is also denoted as " 1233yd to 3,3- trifluoro propenes (Z) below
(Z) " feedstock composition) simultaneously makes the 1233yd (E) in the feedstock composition that isomerization reaction occur to manufacture 1233yd's (Z)
Method.In addition, the manufacturing method of the 1233yd of another embodiment of the present invention is to make above-mentioned raw materials as shown in following formula [2]
Method of the isomerization reaction to manufacture 1233yd (E) occurs for the 1233yd (Z) in composition.
[changing 1]
[changing 2]
Isomerization reaction shown in above-mentioned formula [1] and [2] between 1233yd (E) and 1233yd (Z) is balanced reaction.This
The manufacturing method of the 1233yd of embodiment is under the condition (being also denoted as " isomerisation conditions " below) that the isomerization reaction occurs
Carry out isomerization reaction.In addition, isomerization reaction shown in above-mentioned formula [1] or formula [2] is also abbreviated as that " isomerization is anti-following
It answers ".
1233yd (Z) and 1233yd (E) is in the equilibrium state of the isomerization reaction with defined molar ratio (balance
Than) exist.In the present specification, equilibrium ratio refers to " 1233yd (Z) and 1233yd (E) under the equilibrium state of isomerization reaction
Molar ratio ", with [(molal quantity of the 1233yd (Z) in 1233yd)/(1233yd's (E) in 1233yd under the equilibrium state
Molal quantity)] it indicates.Reaction temperature (being also denoted as isomerization reaction temperature below), pressure when equilibrium ratio is because of isomerization reaction etc.
And it is different.
For example, the equilibrium ratio at atmospheric pressure and 20 DEG C of isomerization reaction temperature is 97/3 or so.In addition, in atmospheric pressure
And the equilibrium ratio at 230 DEG C of isomerization reaction temperature is 91/9 or so.Hereinafter, " 1233yd (Z)/1233yd (E) " is indicated
The molar ratio of 1233yd (Z) and 1233yd (E).
Herein, 1233yd (Z) is deposited relative to 1233yd (E) and the total of 1233yd (Z) under each isomerization reaction temperature
Fig. 1 is shown in ratio (mole %).As shown in Figure 1, isomerization reaction temperature increases, then 1233yd (Z) there are ratio reduction,
Equilibrium ratio becomes smaller.
In the manufacturing method of the 1233yd (Z) of present embodiment, isomery is less than by using 1233yd (Z)/1233yd (E)
The feedstock composition for changing the equilibrium ratio under reaction temperature, can manufacture 1233yd (Z).That is, passing through above-mentioned isomerization reaction temperature
Under isomerization reaction, 1233yd (Z) in reaction product containing than relative in feedstock composition containing than becoming
It is higher, so that 1233yd (Z) be made.For example, the manufacturing method of the 1233yd (Z) using present embodiment, by by condition most
Optimization can make the content of the 1233yd (Z) in reaction product reach 1233yd (Z) and 1233yd (E) with easy operation
80 moles of % or more of total amount.
On the other hand, in the manufacturing method of the 1233yd (E) of present embodiment, by using 1233yd (Z)/1233yd
(E) it is greater than the feedstock composition of the equilibrium ratio at a temperature of isomerization reaction, 1233yd (E) can be manufactured.That is, passing through above-mentioned isomery
Change the isomerization reaction under reaction temperature, the 1233yd's (Z) in reaction product contains than relative in feedstock composition
Containing than becoming lower, so that 1233yd (E) be made.
As such, in the manufacturing method of present embodiment, by adjusting 1233yd (Z)/1233yd in feedstock composition
(E), it can selectively carry out from 1233yd (E) to the reaction of 1233yd (Z) and from 1233yd (Z) to 1233yd's (E)
Any one of reaction reaction.
In addition, 1233yd (the Z)/1233yd (E) and the difference of the equilibrium ratio under isomerisation temperature in feedstock composition are small
In the case where, compared with the big situation of the difference, the apparent conversion ratio between 1233yd (Z) and 1233yd (E) (Japanese: is shown in か
け up conversion rate) it reduces.But as described later, anti-by repeating above-mentioned isomerization when manufacturing 1233yd (Z)
It answers, the resulting 1233yd of isomerization reaction (Z) is separated with the distillation of 1233yd (E), distilled separating obtained 1233yd (E) again
Isomerization can obtain 1233yd (Z) by 1233yd (E) in industrial advantageous and efficient method.When manufacturing 1233yd (E)
It is also the same such.
[feedstock composition]
In the manufacturing method of present embodiment, feedstock composition (is rubbed with being different from the equilibrium ratio at a temperature of isomerization reaction
Your ratio) molar ratio contain 1233yd (E) and 1233yd (Z).Feedstock composition other than 1233yd (E) and 1233yd (Z),
Also containing the impurity in addition to 1233yd (E) and 1233yd (Z).As the impurity contained in feedstock composition, can enumerate
The manufacture raw material of 1233yd (E) and 1233yd (Z), manufacture 1233yd (E) and 1233yd (Z) Shi Shengcheng remove 1233yd (E) and
By-product etc. other than 1233yd (Z).In addition, in the feelings for carrying out isomerization reaction using the feedstock composition containing above-mentioned impurity
Under condition, the by-product generated by above-mentioned impurity can be removed by existing methods such as distillations.As impurity, preferably exist
Inert compound under conditions of 1233yd (E) or 1233yd (Z) generation isomerization reaction.
1233yd (E) and 1233yd (Z) can be manufactured by well known method.For example, keeping HCFC-244ca anti-with hydrogen fluoride
It answers, 1233yd when can obtain manufacturing HCFC-245ca as by-product.
The resulting 1233yd of above method can be used directly as feedstock composition, can also pass through method well known to distillation etc.
By the E body of 1233yd and Z body separation and by required mixing ratio be configured to feedstock composition come using.
Further, in the resulting composition of above method, other than 1233yd, also containing as product
HCFC-245ca, as manufacture raw material HCFC-244ca, in manufacturing process as by-product generation the chloro- 3,3- difluoro of 1-
Propylene etc..The composition can be used directly as feedstock composition.
The manufacturing method of present embodiment can be batch-type, any method in continuous flow mode.It is imitated from manufacture
From the point of view of rate, the manufacturing method of present embodiment is preferably continuous flow mode.
[isomerisation conditions]
As described above, 1233yd (Z)/1233yd (E) e.g. in feedstock composition is small when manufacturing 1233yd (Z)
The condition of equilibrium ratio at a temperature of defined isomerization reaction.On the other hand, when manufacturing 1233yd (E), e.g. raw material
1233yd (Z)/1233yd (E) in composition is greater than the condition of the equilibrium ratio at a temperature of defined isomerization reaction.
In addition, making the raw material for meeting above-mentioned condition with defined isomerisation conditions in the manufacturing method of present embodiment
Isomerization reaction occurs for composition, the compound needed for capable of being manufactured whereby by above-mentioned isomerization reaction.In addition, by making original
Method that feed composition contacts in reactor with metallic catalyst makes feedstock composition and radical initiator in reactor
The method of contact or the method etc. for heating feedstock composition, can promote isomerization reaction.It, can be quick by these methods
Ground carries out isomerization reaction to reach equilibrium state.Therefore, the above method is suitable for industrially making 1233yd (E) isomerization
To manufacture 1233yd (Z) or make method of 1233yd (Z) isomerization to manufacture 1233yd (E).
In the manufacturing method of present embodiment, isomerization reaction can carry out under liquid phase, can also carry out under gas phase.With
The case where being reacted under gas phase is compared, and in the case where reaction under liquid phase, having can be when manufacturing the object of equivalent
The advantages of being reacted in the reactor of small size.On the other hand, compared with the case where being reacted under liquid phase, the feelings reacted under gas phase
Under condition, the reaction time can be shortened and can inhibit 1,2,3- tri- as by-product chloro- 3- fluoropropenes (ClCHF-CCl by having
=CHCl) generation the advantages of and the unit time object manufacture increase the advantages of.
[reactor]
Reactor used in manufacturing method as present embodiment, as long as being resistant to the temperature in aftermentioned reactor
The reactor of degree and pressure, is not particularly limited, and can use the vertical response of such as glass flask or autoclave, cylindrical shape
Device.As the material of reactor, can be used glass, iron, nickel, using iron or nickel as alloy of principal component etc..In addition, reactor can also
Have to the electric heater etc. heated in reactor.
< has used the isomerization > of metallic catalyst
, it is preferable to use metallic catalyst carries out isomerization reaction in the manufacturing method of present embodiment.By using metal
Catalyst can be improved reaction speed and improve manufacture efficiency.Metallic catalyst has catalytic action for isomerization reaction.Make
For metallic catalyst, such as metal (metal simple-substance or alloy), metal oxide, metal halide can be enumerated etc..Metal catalytic
Agent can be used alone a kind, can also be applied in combination with two or more.
Wherein, from the point of view of efficiently carrying out isomerization reaction, preferably metal oxide or metal halide.
As the metal for constituting metallic catalyst, transition metal element, the 12nd race's metallic element, the 13rd race's metal can be enumerated
Element, the 14th race's metallic element, the 15th race's metallic element.Wherein, preferably group-4 metal element, the 6th race's metallic element, the 8th
Race's metallic element, the 9th race's metallic element, the 10th race's metallic element, the 11st race's metallic element, the 12nd race's metallic element, the 13rd race
Metallic element, the 14th race's metallic element, the 15th race's metallic element, preferably group-4 metal element, the 6th race's metallic element, the 8th race
Metallic element, the 10th race's metallic element, the 11st race's metallic element, the 12nd race's metallic element, the 13rd race's metallic element.
The metal for constituting metallic catalyst is transition metal element, the 12nd race's metallic element, the 13rd race's metallic element, the 14th
In the case where race's metallic element, the 15th race's metallic element, it is more preferably selected from titanium (Ti), zirconium (Zr), hafnium (Hf) (group-4 metal member
Element), niobium (Nb), tantalum (Ta) (the 5th race's metallic element), chromium (Cr), tungsten (W) (the 6th race's metallic element), rhenium (Re) (the 7th race's metal
Element), iron (Fe), ruthenium (Ru) (the 8th race's metallic element), cobalt (Co), rhodium (Rh) (the 9th race's metallic element), nickel (Ni), palladium
(Pd), platinum (Pt) (the 10th race's metallic element), copper (Cu) (the 11st race's metallic element), zinc (Zn) (the 12nd race's element), boron (B),
Aluminium (Al), gallium (Ga), indium (In) (the 13rd race's metallic element), tin (Sn) (the 14th race's metallic element), antimony (Sb) (the 15th race's metal
Element) at least one kind of element.
Metallic catalyst can be one of above-mentioned metal, be also possible to the alloy of two or more metals.Metal oxygen
Compound can be the oxide of above-mentioned a kind of metal, be also possible to the composite oxides of metal of more than two kinds.Metal halide can
To be the halide of above-mentioned a kind of metal, it is also possible to the complex halide of metal of more than two kinds.
In addition, metallic catalyst can also be supported in carrier.As carrier, such as alumina support, zirconium oxide load can be enumerated
Body, silica supports, silica alumina support, using active carbon as the carbon carrier of representative, barium sulfate carrier, calcium carbonate carry
Body etc..As active carbon, it can enumerate and prepare and obtain such as the raw material as timber, charcoal, shell, coconut husk, peat, lignite, coal
Active carbon etc..In the case that carrier is the compound of the same race with metallic catalyst, there can also be the function as metallic catalyst
Energy.
In addition, metallic catalyst preferably implements activation in advance from the point of view of improving reactivity.As
The method of activation can enumerate the side under heating or contacting metallic catalyst with activation agent
Method.As activation agent, can be used such as hydrogen fluoride, hydrogen chloride, hydrofluorocarbons.Activation agent can be used alone
It a kind, can also be applied in combination with two or more.Wherein, it is preferable to use hydrofluorocarbons are as activation agent.It is activated as being used as
The hydrofluorocarbons of inorganic agent suitably have such as trichlorofluoromethane (CFC-11), dicholorodifluoromethane (CFC-12), trifluorochloromethane
(CFC-13), dichlorofluoromethane (HCFC-21), difluorochloromethane (HCFC-22), fluoroform (HFC-23), tetrafluoroethene
(FO-1114) etc..In addition, the 1233yd (E) or 1233yd (Z) in feedstock composition can also be used for activation agent.
In addition, other than the activation before this reaction, additionally it is possible to be activated place again to metallic catalyst
Reason.That is, in isomerization reaction, preferably reduce in the activity of metallic catalyst, the conversion speed between the E body and Z body of 1233yd
Activation again is carried out to metallic catalyst (when the spent time is elongated until reaching isomerization equilibrium) when degree reduces.By
This makes the activation recovering of metallic catalyst, can reuse metallic catalyst.
It is identical as the activation before using as the method for activation again, can enumerate under heating or it is non-plus
The method for contacting metallic catalyst with activation agent.It is (active again as the inorganic agent for activation again
Change inorganic agent), oxygen, hydrogen fluoride, hydrogen chloride, chlorinated and fluorinated hydrocarbon etc. can be used.As chlorinated and fluorinated hydrocarbon, the portion of hydrocarbon can be enumerated
Compound obtained by point hydrogen is replaced by chlorine, replaced by fluorine obtained by compound, replaced by chlorine and fluorine obtained by compound, can enumerate
Carbon tetrachloride, chloroform, methylene chloride (HCC-30), chloromethanes, vinyl chloride, CFC-11, CFC-12, CFC-13, HCFC-21,
HCFC-22, HFC-23, FO-1114,1233yd (E), 1233yd (Z) etc..In addition, in activation again, from side reaction
Inhibit and the raising of the durability of metallic catalyst angularly considers, in order to dilute activation agent again, nitrogen, argon can be used
The inert gases such as gas, helium.
Metallic catalyst can carry out activation before accommodating into reactor, for easy to operate and operating efficiency
Good consideration, preferably to accommodate state implementation activation in the reactor.It is therefore preferable that metal catalytic is accommodated
Activation agent is imported in the reactor of agent to implement activation.Activation agent can be imported directly instead at normal temperature
Device is answered, from the point of view of improving reactivity, temperature adjusting is preferably implemented by heating etc. when importing reactor.
In addition, implementing in the state of preferably heating in reactor to improve the efficiency of activation
Activation.In this case, it is preferred that the temperature in reactor is heated to 50~400 DEG C.
(isomerization under liquid phase)
In the case that the manufacturing method of the 1233yd of present embodiment is implemented under liquid phase, the material combination of liquid can be made
Object is contacted in reaction vessel with metallic catalyst to implement.
In the case that the manufacturing method of the 1233yd of present embodiment is implemented under liquid phase, preferably metal halide is as gold
Metal catalyst.Wherein, it more preferably uses containing at least 1 selected from Al, Sb, Nb, Ta, W, Re, B, Sn, Ga, In, Zr, Hf and Ti
The halide of kind element.
As metal halide, it is able to use GaCl2、GaCl3、ZrCl4、BCl3、AlCl3、HfCl4、InCl3、TiCl4Deng
Metal chloride or these metal chlorides it is a part of it is perfluorinated obtained by compound, such as AlFCl2、AlF2Cl、
TiCl2F2、TiClF3、ZrCl2F2、ZrCl2F、ZrClF2Deng.In addition, being able to use GaBr as metallic catalyst3、GaI3、
HfBr4、InI3、TiBr4A part of equal metal bromides, metal iodide or these metal bromides, metal iodide passes through
Compound obtained by above-mentioned activation etc. is chlorinated, is fluorinated.Wherein, from the angle that can be carried out efficiently isomerization reaction
Consider, preferred metal chloride it is a part of it is perfluorinated obtained by compound, such as AlFCl2、AlF2Cl。
Total amount of the additive amount of this metallic catalyst relative to 1233yd (E) and 1233yd (Z) in feedstock composition
(100 mass %) is preferably calculated as 1~100 mass %, more preferably 5~50 mass % with outside addition (Japanese: adding outside), into one
Step is preferably 5~15 mass %.If it is above range, then it can be carried out efficiently isomerization reaction.
In the case that the manufacturing method of present embodiment carries out under liquid phase, preferably addition reaction dissolvent is to control reaction
Heat.In the case where stating metallic catalyst in use, reaction dissolvent is the compound inert to metallic catalyst, makes starting material
Matter and target product dissolution, but insoluble metallic catalyst.Moreover, being easily to be separated by distillation etc. with object
Compound.This reaction dissolvent is, for example, the organic solvent for the aprotic that boiling point is 60 DEG C~200 DEG C, specific preferred tetrachloro
Change carbon, chloroform etc..
Reaction condition when carrying out isomerization reaction under liquid phase using metallic catalyst is, reaction temperature is preferably 0~
150 DEG C, more preferably 10~100 DEG C, further preferably 10~50 DEG C.If it is above range, then can be carried out efficiently
Isomerization reaction.Reaction time is different because of reaction temperature and the type of metallic catalyst, from the point of view of manufacture efficiency, usually
Preferably 0.5~200 hour, particularly preferably 1~100 hour, more preferably 1~10 hour.
(isomerization under gas phase)
In the case that the manufacturing method of the 1233yd of present embodiment is implemented under gas phase using metallic catalyst, it can make
Feedstock composition is contacted in reaction vessel with metallic catalyst to implement isomerization reaction.Specifically, can for example pass through
Metallic catalyst is accommodated in reactor and forms reacting part, feedstock composition is made to circulate in the reacting part to be reacted.
In this case, metallic catalyst can be accommodated in a manner of any in fixed-bed type or fluidized bed type.In addition, in fixed-bed type
In the case of, it can be any one of horizontal fixed-bed type and vertical fixed-bed type.Above-mentioned isomerization reaction generate by mostly at
When dividing the mixed gas constituted, it is easy to prevent from causing because of difference in specific gravity each ingredient to form concentration distribution at each position, therefore metal is urged
Agent is preferably vertical fixed-bed type.Hereinafter, the side of the manufacturing method for the 1233yd for carrying out present embodiment under gas phase
Method carries out the manufacturing method of present embodiment in a manner of continuous flow, feedstock composition is with the state and metal catalytic of gas phase
Reaction condition when agent contacts and carries out isomerization reaction is illustrated, but the present invention is not limited.
, it is preferable to use metal simple-substance or metal oxide in the case that the manufacturing method of present embodiment carries out under gas phase
As metallic catalyst.Can specifically enumerate iron, cobalt, nickel, palladium, chromium oxide (chromia), aluminium oxide (alumina), zinc oxide,
Ferric flouride, aluminum fluoride, aluminium chloride, charomic fluoride, chromium chloride etc..It is examined from the angle for being easy to get and efficiently carry out isomerization reaction
Consider, preferred aluminium oxide and chromium oxide in these metallic catalysts.
When the manufacturing method of the 1233yd of present embodiment is implemented under gas phase, from the inhibition of side reaction, initial substance to
The adjustment of the supply easness, flow of reactor angularly considers, preferably by feedstock composition and diluent gas be commonly fed to
Reactor.In addition, also being had in the case where carrying out isomerization reaction in the presence of above-mentioned metallic catalyst using diluent gas
The advantages of improving the durability of metallic catalyst.
As diluent gas, can enumerate nitrogen, carbon dioxide gas, rare gas (helium etc.), to above embodiment
The gas etc. of the inert organic compound of isomerization reaction.As inert organic compound, can enumerate methane, ethane, propane,
The saturated hydrocarbons such as butane, pentane, hexane, fluoroform (HFC-23), difluoromethane (HFC-32), pentafluoroethane (HFC-125), four
Fluoroethane (HFC-134 or HFC-134a), trifluoroethane (HFC-143 or HFC-143a), Difluoroethane (HFC-152 or HFC-
152a), the fluorohydrocarbons such as tetrafluoropropane (HFC-254eb etc.).The amount of diluent gas is not particularly limited, specifically, relative to confession
To the feedstock composition (100 moles of %) to reactor, preferably 1~10000 mole of %, more preferably 10~1000 rub
The amount of that %, further preferably 30~500 moles of %, most preferably 50~150 moles of %.Diluent gas can be used alone 1
Kind, it can also be applied in combination with two or more.
In the case that the manufacturing method of present embodiment carries out under gas phase, imported again after feedstock composition can also being preheated
Reactor.From the point of view of gasifying to improve reactivity from the 1233yd (E) and 1233yd (Z) that make in feedstock composition, at this time
Preheating temperature be preferably 20~300 DEG C, more preferably 50~250 DEG C.
In addition, using diluent gas, from the point of view of improving reactivity, feedstock composition and carrier gas
Body preferably imports reactor after the preheating of above-mentioned preferable temperature again.Feedstock composition can be pre- through above-mentioned temperature respectively with diluent gas
It remixed after heat, be then supplied to reactor, preheated again after can also mixing feedstock composition with diluent gas and supplied to anti-
Answer device.
The reaction in reaction condition in the manufacturing method of present embodiment, when for carrying out isomerization reaction under gas phase
Pressure, such as the purpose of shortening the reaction time and in the case where must pressurizeing, can be 1.0MPa pressurization item below
Part makes internal pressure normal pressure~1.0MPa pressure condition in reactor.It is excellent from the point of view of the easness industrially implemented
It is selected under normal pressure or 0.2MPa micro- pressurization below and is reacted.Normal pressure refers to atmospheric pressure.
The Contact Temperature (reaction temperature) of feedstock composition and metallic catalyst indicates preferably 0 with the temperature in reactor
~500 DEG C, more preferably 50~350 DEG C, further preferably 100~260 DEG C, most preferably 150~250 DEG C.Reaction temperature
If can be carried out efficiently isomerization reaction more than above-mentioned lower limit value.On the other hand, if reaction temperature is on above-mentioned
Limit value is hereinafter, be then able to suppress the case where causing by-product to generate by the decomposition of 1233yd (E) and 1233yd (Z).In reactor
Feedstock composition and time of contact (reaction time) of metallic catalyst be preferably 0.1~1000 second, more preferably 1~100
Second.In addition, time of contact is equivalent to residence time of the feedstock composition in reactor, can by adjust feedstock composition to
The supply amount (flow) of reactor is controlled.
< is contacted with radical initiator and the isomerization > that carries out
In the manufacturing method of present embodiment, above-mentioned isomerization reaction can be by causing feedstock composition and free radical
Agent contacts to carry out.Radical initiator is activated by heat or light, is generated free radicals.As making feedstock composition and free radical
Initiator contact can enumerate the free radical for making feedstock composition and activating through heat or light come the method for carrying out isomerization reaction
The method that initiator contacts in reactor.In this case, isomerization reaction preferably carries out under gas phase.
Radical initiator can be by the activation of any one of heat or light, and also can be used in combination the two.Industrially, excellent
Choosing is only activated with heat, to heated heater fed feedstock composition with the mixture of radical initiator to react
The method simplicity for assigning thermal energy to the mixture in device, being activated radical initiator with heat, therefore preferably.
Radical initiator carries out illumination through light and in the case where activating, to radical initiator.As being irradiated
Light, can specifically enumerate ultraviolet light and the visible light etc. including the light of 200~400nm of wavelength.As institute in this illumination
Light source can be enumerated such as high-pressure sodium lamp, low pressure mercury lamp, metal halide lamp.
As the method for light irradiation, wavelength needed for will being for example equipped with the above-mentioned isomerization reaction of at least transmissive can be enumerated
The light source intercalation reaction ingredient of light, the collet being made of material inert and corrosion resistance to ingredient present in reaction system
From inside reactor to the method for reacted constituent irradiation light etc. in gas.In addition, in the case that light source generates heat, based on reaction
Temperature, preferably above-mentioned collet are the collets with cooling element.
Free radical is that have the chemical substances such as the atom, molecule or ion of unpaired electron (Japanese: chemical seed), chemicals
The charge of matter includes that positive radical cation, the charge free radical anion, the charge that are negative are neutral free radical, double freedom
Base, carbene etc..Fluoro free radical, chlorine radical, bromine free radical, iodine free radical, oxygen radical, hydroperoxyl radical, hydroxyl can specifically be enumerated
Base free radical, nitro free radical, nitrogen free radical, alkyl diradical, difluorocarbene or carbon radicals etc..
As the radical initiator for generating free radical as described above, has and produced by assigning the external energies such as light and heat
The compound in addition to 1233yd (E) and 1233yd (Z) of raw free radical.As radical initiator, chlorine, bromine can be specifically enumerated
Equal halogen gas or halogenated hydrocarbon etc., air, oxygen, ozone, hydrogen peroxide etc..Halogenated hydrocarbon be with methane, ethane, propane, butane,
The hydrogen atom that carbon atom in the olefines such as the alkanes such as pentane, hexane and ethylene, propylene, butylene, amylene, hexene combines
Halogenated hydrocarbon obtained by part or all is replaced by fluorine, chlorine, bromine or iodine atom, the halogenated hydrocarbon contain fluorine, chlorine, in bromine or iodine extremely
It is a kind few.Radical initiator can be used alone, and can also be applied in combination with two or more.
As radical initiator, in above-mentioned substance, from cheap and from the point of view of being easy to get, preferably oxygen, air and
Chlorine.Wherein, from the point of view of being easy to produce free radical, preferably chlorine.In addition, being examined from the segregative angle of product
Consider, radical initiator is preferably air or oxygen.
Supply to reactor radical initiator amount be preferably it is micro.Reason is that the generation of free radical is continuous
's.In addition, the radical initiator of addition surplus not only results in the waste of secondary material, it can also be to the target substance after reaction
Or the separation process of initial substance and radical initiator causes to bear.
Isomerization > caused by < is heated
Isomerization reaction in the manufacturing method of the 1233yd of present embodiment can by the temperature of feed change composition,
Such as it is carried out by heating.It, can be by heating raw material in reactor in the case where carrying out isomerization reaction by heating
Composition carries out.Specifically, heating base feed for example into the reactor heated with heating furnaces such as electric furnaces
Composition.In this case, isomerization reaction preferably carries out under gas phase.
In the case where carrying out isomerization reaction by heating, reaction pressure is identical as the case where using metallic catalyst, excellent
It is selected as normal pressure or 0.2MPa micro- pressurization below.Heating temperature (reaction temperature) is preferably 400~1000 DEG C, more preferable 400~
900℃.The residence time (reaction time) of feedstock composition in reactor is preferably 0.001~1000 second, more preferably
0.01~100 second.By improving reaction temperature in above-mentioned preferred scope or extending the reaction time to improve turn between isomers
Rate can be obtained with the equilibrium ratio of the reaction temperature or the 1233yd for containing isomers close to the ratio of the equilibrium ratio.
(reaction product)
In the manufacturing method of present embodiment, it can obtain from the reaction product that reactor flows out as object
1233yd (E) or 1233yd (Z).In reaction product, sometimes with the pair of the generations such as the impurity as contained by feedstock composition
Product or the by-product generated by the decomposition of 1233yd (E) or 1233yd (Z).By-product is specially the chloro- 3- fluorine of 1,2,3- tri-
Propylene etc..These by-products in reaction product can be removed by method known to distillation etc. to required degree.
In addition, in above-mentioned isomerization reaction, as described above, having reached the equilibrium-like of isomerization reaction under isomerization conditions
State, therefore even if adjusting to suitable reaction condition (isomerisation conditions), also contain other than target substance in reaction product
There is initial substance.That is, containing both 1233yd (E) and 1233yd (Z) in reaction product.
The boiling point of 1233yd (E) and 1233yd (Z) in reaction product have differences, therefore can use common distillation
Method is separated.Therefore, sour cleaning, alkali cleaning, synthetic zeolite etc. are carried out to reaction product obtained as above as needed
The dehydration of adsorbent, the removing of by-product, distillation, can respectively obtain the 1233yd (E) and 1233yd (Z) of high-purity whereby.
Specifically, supplying the reaction product containing 1233yd (E) and 1233yd (Z) for implementing above-mentioned cleaning etc. to destilling tower
It is distilled, the distillate with 1233yd (E) for principal component can be obtained from tower top respectively, obtain (Z) containing 1233yd from tower bottom
Basic sediment (Japanese: narrow-necked earthen jar goes out object).
For example, in the case where object is 1233yd (Z), distill the 1233yd (Z) that contains in resulting distillate/
1233yd (E) is less than equilibrium ratio.Therefore, by using and being measured in the same manner as described above different as feedstock composition using the distillate
Structureization reaction, can be converted into 1233yd (Z) for the 1233yd (E) in distillate.
On the other hand, it in the case where object is 1233yd (E), distills and contains in resulting basic sediment
1233yd (Z)/1233yd (E) is greater than equilibrium ratio.Therefore, by basic sediment is used as feedstock composition and with it is above-mentioned
It is carried out similarly isomerization reaction, the 1233yd (Z) in distillate can be converted into 1233yd (E).
It, being capable of efficiently manufacturing objective object as such, by repeating isomerization reaction and distillation.
More than, by the manufacturing method of present embodiment, by feedstock composition for different under defined isomerisation conditions
1233yd (E) isomerization can be manufactured 1233yd (Z) in industrial advantageous and efficient method by structureization reaction, or will
1233yd (Z) isomerization is to manufacture 1233yd (E).
Embodiment
[analysis condition]
In the manufacture of various compounds below, the composition analysis of resulting reaction product has used gas-chromatography
(GC).Use DB-1301 (long 250 μ m of 60m × internal diameter thickness 1 μm, Agilent Technologies (ア ジ レ Application ト テ Network ノ ロ ジ
ー Co., Ltd.) system) it is used as column.
[manufacture of 1233yd (Z)]
(embodiment 1)
Firstly, metallic catalyst is activated as follows.That is, on 3 mouthfuls of flasks (internal volume 50mL) setting make it is cold
But the alchlor of 100g (0.75 mole) is added in the Di Muluo condenser of extremely -20 DEG C of refrigerant cycle thereto
(AlCl3), after being cooled to 0 DEG C, slowly the dichlorofluoromethane (CHFCl that 230g (2.2, mole) is added dropwise while stirring2)。
The isomerization of dichlorofluoromethane is carried out along with the generation of low-boiling point gas.Then, it is carried out in isomerization same
When, in the alchlor (AlCl as metallic catalyst3) and as between the dichlorofluoromethane of activation agent carry out halogen
Plain exchange reaction generates fluorine-substituted aluminum halide.Reaction removes volatile ingredient after continuing 1 hour, and metallic catalyst is dry.According to
This, has obtained partially fluorinated aluminium chloride.
Then, 1g is added in the glass reactor (internal volume 50mL) for being provided with the Di Muluo condenser for being cooled to 0 DEG C
The resulting partially fluorinated aluminium chloride of above-mentioned reaction as metallic catalyst, then 10g carbon tetrachloride is added thereto as solvent.
Then, the temperature of reactor is set as 20 DEG C, be slowly added into as the E body of 1233yd and the mixture of Z body and Z body and E body
Molar ratio (1233yd (Z)/1233yd (E)) is the feedstock composition 10g (0.08 mole) of 0.01/99.99, is reacted while stirring
1 hour.The composition (molar ratio) of feedstock composition used in embodiment 1 is shown in table 1.
Liquid after filtering reaction has recycled the reaction product 20g as liquid phase to remove metallic catalyst.Then,
Using the liquid phase of the resulting reaction product of chromatographic, the composition of reaction product has been found out.As a result with reaction item
Part is shown in table 1 together.
[table 1]
(embodiment 2)
In addition to changing the E body of the 1233yd in feedstock composition and containing than other than for Z body, according to same with embodiment 1
The step of sample, has carried out isomerization reaction.Composition, reaction condition and the result of feedstock composition are shown in table 2.
[table 2]
(embodiment 3,4)
Firstly, metallic catalyst is activated as follows.That is, by granulated active alumina (diameter 3mm, high 3mm, ratio
Surface area 160m2/ g, RiHui catalyst synthesis Co., Ltd (waving catalyst chemical conversion society day) system, product name N612N) it fills to internal diameter
The reaction tube (reactor) processed of Inconel (イ Application U ネ Le (registered trademark)) 600 of 2.54cm, long 100cm, are impregnated in salt bath
In.By salt bath heating to 250 DEG C, nitrogen/HCFC-22 (CHClF for circulating 10 hours in reactor2) 2/1 (molar ratio)
Mixed gas, activate metallic catalyst.
Then, the salt temperature (reaction temperature) of embodiment 3 is set as 230 DEG C, the salt temperature of embodiment 4 is set
It is 280 DEG C.In addition, stopping the supply of HCFC-22, supplied into reactor and reality with 20 seconds times of contact (reaction time)
Apply the mixed gas of 1 same feedstock composition and nitrogen of example.The condition described in table 3 flows feedstock composition in reactor
Pass to carry out isomerization reaction.By the gas composition of gas chromatographic analysis reactor outlet, reaction product is analyzed whereby
Composition.Composition, reaction condition and the analysis result of feedstock composition are shown in table 3.
(embodiment 5)
Other than metallic catalyst is not used, reaction temperature is changed to 400 DEG C, pass through item similarly to Example 3
Part has carried out isomerization reaction.Composition, reaction condition and the analysis result of feedstock composition are shown in table 3.
[table 3]
(embodiment 6)
In addition to changing the E body of the 1233yd in feedstock composition and containing than other than for Z body, according to same with embodiment 3
The step of sample, has carried out isomerization reaction.Composition, reaction condition and the analysis result of feedstock composition are shown in table 4.
[table 4]
[manufacture of 1233yd (E)]
(embodiment 7)
1g is added in the glass reactor (internal volume 50mL) for being provided with the Di Muluo condenser for being cooled to 0 DEG C as gold
The resulting partially fluorinated aluminium chloride of the above-mentioned reaction of metal catalyst, then 10g carbon tetrachloride is added thereto as solvent.Then,
The temperature of reactor is set as 20 DEG C, is slowly added into as the E body of 1233yd and the mixed liquor of Z body and Z body and E body molar ratio
(1233yd (Z)/1233yd (E)) is the feedstock composition 10g (0.08 mole) of 99.99/0.01, is reacted 1 hour while stirring.
The composition of feedstock composition is shown in table 5.
Then, the liquid after filtering reaction has recycled the reaction product 20g as liquid phase to remove metallic catalyst.
Then, using the liquid phase of the resulting reaction product of chromatographic, the composition of reaction product has been found out.Analyze result
It is shown in table 5 together with reaction condition.
[table 5]
(embodiment 8)
Other than the composition for changing feedstock composition, according to similarly to Example 7 the step of to have carried out isomerization anti-
It answers.Composition, reaction condition and the analysis result of feedstock composition are shown in table 6.
[table 6]
(embodiment 9,10)
Use above-mentioned resulting activation aluminium oxide as metallic catalyst similarly to Example 3.In addition, with implementation
The reaction temperature of embodiment 9 is similarly set as 230 DEG C by example 3, and the reaction temperature of embodiment 10 is set as 280 DEG C, by table 7
The feedstock composition of shown composition and the mixed gas of nitrogen are supplied to reactor.The condition described in table 7 makes feedstock composition
Circulation is in reactor to carry out isomerization reaction.By the gas composition of gas chromatographic analysis reactor outlet, analyze whereby
The composition of reaction product.Composition, reaction condition and the analysis result of feedstock composition are shown in table 7.
(embodiment 11)
Other than metallic catalyst is not used, reaction temperature is changed to 400 DEG C, according to step similarly to Example 9
Suddenly isomerization reaction has been carried out.Composition, reaction condition and the analysis result of feedstock composition are shown in table 7.
[table 7]
(embodiment 12)
Other than the composition for changing feedstock composition, according to similarly to Example 9 the step of to have carried out isomerization anti-
It answers.Composition, reaction condition and the analysis result of feedstock composition are shown in table 8.
[table 8]
By table 1~8 it is found that by under defined isomerisation conditions by feedstock composition for isomerization reaction, can
Isomerization reaction is set to carry out and manufacture 1233yd (Z) or 1233yd (E).
Claims (15)
1.1- chloro- 2, the manufacturing method of 3,3- trifluoro propenes (Z), which is characterized in that make to be different from defined isomerization reaction
At a temperature of the molar ratio of equilibrium ratio (molar ratio) contain the chloro- 2,3,3- trifluoro propene (E) of 1- and the chloro- 2,3,3- trifluoro propene of 1-
(Z) the chloro- 2,3,3- trifluoro propene (E) of the 1- in feedstock composition carries out isomerization at a temperature of the isomerization reaction
Reaction is to manufacture the chloro- 2,3,3- trifluoro propene (Z) of 1-.
2. 1- chloro- 2 as described in claim 1, the manufacturing method of 3,3- trifluoro propenes (Z), which is characterized in that the raw material group
It closes in object, the 1- chloro- 2,3,3- trifluoro propenes (Z) and the 1- chloro- 2, the molar ratios of 3,3- trifluoro propenes (E) (1- chloro- 2,
The chloro- 2,3,3- trifluoro propene (E) of 3,3- trifluoro propene (Z)/1-) be less than the isomerization reaction at a temperature of equilibrium ratio (mole
Than).
3. 1- chloro- 2 as claimed in claim 1 or 2, the manufacturing method of 3,3- trifluoro propenes (Z), which is characterized in that described different
Structureization reaction is by carrying out the feedstock composition and metallic catalyst and contact.
4. 1- chloro- 2 as claimed in claim 3, the manufacturing method of 3,3- trifluoro propenes (Z), which is characterized in that the metal is urged
Agent is at least one kind of substance in metal simple-substance, alloy, metal oxide and metal halide.
5. 1- as described in claim 3 or 4 chloro- 2, the manufacturing method of 3,3- trifluoro propenes (Z), which is characterized in that constitute institute
The metal for stating metallic catalyst is selected from group-4 metal element, the 6th race's metallic element, the 8th race's metallic element, the 9th race's metal member
At least one kind of member in element, the 10th race's metallic element, the 11st race's metallic element, the 12nd race's metallic element and the 13rd race's metallic element
Element.
6. the 1- chloro- 2 as described in any one of claim 3~5, the manufacturing method of 3,3- trifluoro propenes (Z), feature exist
In the metallic catalyst is at least one kind of compound in metal oxide and metal halide.
7. the 1- chloro- 2 as described in any one of claim 4~6, the manufacturing method of 3,3- trifluoro propenes (Z), feature exist
In the metal oxide is at least one kind of in aluminium oxide and chromium oxide.
8. the 1- chloro- 2 as described in any one of claim 4~6, the manufacturing method of 3,3- trifluoro propenes (Z), feature exist
In the metal halide is compound obtained by a part of metal chloride is fluorinated.
9. the manufacturing method of 3,3- trifluoro propenes (Z), feature exists such as 1- according to any one of claims 1 to 8 chloro- 2
In the isomerization reaction temperature is at 0 DEG C or more 500 DEG C or less.
10. the manufacturing method of 3,3- trifluoro propenes (Z), feature exists such as 1- according to any one of claims 1 to 9 chloro- 2
In the isomerization reaction carries out under liquid phase.
11. the manufacturing method of 3,3- trifluoro propenes (Z), feature exists such as 1- according to any one of claims 1 to 9 chloro- 2
In the isomerization reaction carries out under gas phase.
12. 1- chloro- 2 as claimed in claim 11, the manufacturing method of 3,3- trifluoro propenes (Z), which is characterized in that the isomery
Change reaction to carry out in the presence of inert gas.
13. the 1- chloro- 2 as described in claim 11 or 12, the manufacturing method of 3,3- trifluoro propenes (Z), which is characterized in that described
Isomerization reaction is carried out at 0 DEG C or more 260 DEG C or less.
14.1- chloro- 2, the manufacturing method of 3,3- trifluoro propenes (E), which is characterized in that make to be different from defined isomerization reaction
At a temperature of the molar ratio of equilibrium ratio (molar ratio) contain the chloro- 2,3,3- trifluoro propene (E) of 1- and the chloro- 2,3,3- trifluoro propene of 1-
(Z) the chloro- 2,3,3- trifluoro propene (Z) of the 1- in feedstock composition carries out isomerization at a temperature of the isomerization reaction
Reaction is to manufacture the chloro- 2,3,3- trifluoro propene (E) of 1-.
15. 1- chloro- 2 as claimed in claim 14, the manufacturing method of 3,3- trifluoro propenes (E), which is characterized in that the raw material
In composition, the 1- chloro- 2,3,3- trifluoro propenes (Z) and the 1- chloro- 2, (1- is chloro- for the molar ratio of 3,3- trifluoro propenes (E)
The chloro- 2,3,3- trifluoro propene (E) of 2,3,3- trifluoro propene (Z)/1-) it (rubs greater than the equilibrium ratio at a temperature of the isomerization reaction
That ratio).
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| JP2016-177717 | 2016-09-12 | ||
| PCT/JP2017/032837 WO2018047972A1 (en) | 2016-09-12 | 2017-09-12 | 1-chloro-2,3,3-trifluoropropene production method |
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| CN115043701A (en) * | 2022-08-12 | 2022-09-13 | 山东澳帆新材料有限公司 | Preparation method of cis-1-chloro-3, 3, 3-trifluoropropene |
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| JPWO2019189024A1 (en) * | 2018-03-30 | 2021-04-08 | Ａｇｃ株式会社 | Method for producing 1-chloro-2,3,3-trifluoropropene |
| JPWO2022138675A1 (en) * | 2020-12-22 | 2022-06-30 |
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| JPWO2018047972A1 (en) | 2019-06-24 |
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