JP2015120669A - Method for manufacturing (e)-1,3,3,3-tetrafluoropropene - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for manufacturing (E)-1,3,3,3-tetrafluoropropene by using a((E) and/or (Z))-1-chloro-3,3,3-trifluoropropene as a raw material and without using hydrogen fluoride.SOLUTION: There is provided a method for manufacturing (E)-1,3,3,3-tetrafluoropropene by contacting a raw material composition containing at least one kind of ((E) and/or (Z))-1-chloro-3,3,3-trifluoropropene represented and fluorocarbons represented by the following general formula (1): CFClH, where w, x, y and z are all integers and 2≤w≤5, 1≤x≤2w+2, 0≤y<2w+2, 0≤z<2w+2, other than ((E) and/or (Z))-1-chloro-3,3,3-trifluoropropene with a metallic catalyst to convert ((E) and/or (Z))-1-chloro-3,3,3-trifluoropropene to (E)-1,3,3,3-tetrafluoropropene.

Description

  The present invention relates to a method for producing (E) -1,3,3,3-tetrafluoropropene.

  (E) -1,3,3,3-tetrafluoropropene (HFO-1234ze (E)) is a greenhouse gas 1,1,1,2-tetrafluoroethane (R-134a), 1,1 -As a refrigerant, a foaming agent, a cleaning agent, a solvent and an aerosol in place of difluoroethane (R-152a), 1,1,1,3,3-pentafluoropropane (R-245fa), and a raw material monomer of a functional material and In recent years, great expectations have been placed on intermediates for synthesis. In this specification, for halogenated hydrocarbons, the abbreviations of the compounds may be described in parentheses after the compound names, but in this specification, the abbreviations are used instead of the compound names as necessary. . A compound having a notation such as (Z) or (E) after the compound name or after the abbreviation of the compound indicates a Z isomer or E isomer of a geometric isomer.

  As a method for producing HFO-1234ze (E), for example, ((E) and / or (Z))-1-chloro-3,3,3-trifluoropropene (HFO-1233zd (E / Z)) is a catalyst. Reaction with hydrogen fluoride in the presence of an intermediate product containing 1-chloro-1,3,3,3-tetrafluoropropane (R-244fa) and / or R-245fa, A method of dehydrohalogenating a product has been proposed (see, for example, Patent Document 1). In addition, a method of directly obtaining HFO-1234ze (E) by reacting HFO-1233zd (E / Z) with hydrogen fluoride in the presence of a catalyst has been proposed (for example, see Patent Document 2).

  In the conventional method described above, HFO-1234ze (E) can be synthesized using HFO-1233zd (E / Z) as a raw material, but since hydrogen fluoride is used as a reactant, the apparatus and piping are expensive and corrosion-resistant. It was necessary to make it with a simple material. In addition, there is a high risk of accidents caused by hydrogen fluoride, and it takes a lot of effort to manage safety risks in case of leakage. Therefore, there has been a demand for a new and safer method for producing HFO-1234ze (E) from HFO-1233zd (E / Z).

JP 2011-190272 A JP 2004-43410 A

  An object of the present invention is to provide a method for producing HFO-1234ze (E) using HFO-1233zd (E / Z) as a raw material and not using hydrogen fluoride as a raw material.

  The production method of the present invention is represented by ((E) and / or (Z))-1-chloro-3,3,3-trifluoropropene and the following general formula (1) ((E) and / or ( Z)) A raw material composition containing at least one fluorocarbon other than 1-chloro-3,3,3-trifluoropropene is brought into contact with a metal catalyst, so that ((E) and / or (Z) ) -1-chloro-3,3,3-trifluoropropene is converted to (E) -1,3,3,3-tetrafluoropropene.

（ただし、式（１）中、ｗ、ｘ、ｙ、ｚはすべて整数であり、２≦ｗ≦５、１≦ｘ≦２ｗ＋２、０≦ｙ＜２ｗ＋２、０≦ｚ＜２ｗ＋２である。）

(In the formula (1), w, x, y, and z are all integers, and 2 ≦ w ≦ 5, 1 ≦ x ≦ 2w + 2, 0 ≦ y <2w + 2, and 0 ≦ z <2w + 2)

  According to the production method of the present invention, it is possible to produce HFO-1234ze (E) using HFO-1233zd (E / Z) as a raw material and without using hydrogen fluoride as a raw material. The production method of the present invention is excellent in safety.

The figure which shows roughly an example of the reaction apparatus used for the manufacturing method of this invention.

  Embodiments of the present invention will be described below.

(Method for producing HFO-1234ze (E))
The production method of the present invention is at least one of fluorocarbons other than HFO-1233zd (E / Z) and HFO-1233zd (E / Z) represented by the following formula (1) (hereinafter referred to as fluorocarbons (A)). This is a method for producing HFO-1234ze (E) by bringing a raw material composition containing seeds into contact with a metal catalyst to fluorinate and convert HFO-1233zd (E / Z).

(ただし、式（１）中、ｗ、ｘ、ｙ、ｚはすべて整数であり、２≦ｗ≦５、１≦ｘ≦２ｗ＋２、０≦ｙ＜２ｗ＋２、０≦ｚ＜２ｗ＋２である。）

(In the formula (1), w, x, y, and z are all integers, and 2 ≦ w ≦ 5, 1 ≦ x ≦ 2w + 2, 0 ≦ y <2w + 2, and 0 ≦ z <2w + 2)

  The reaction of HFO-1233zd (E / Z) and fluorocarbons (A) in the production method of the present invention can be represented by the following reaction formula (2).

（ただし、式（２）中、ｗ、ｘ、ｙ、ｚ、ｐ、ｑ、ｒはすべて整数であり、２≦ｗ≦５、１≦ｘ≦２ｗ＋２、０≦ｙ＜２ｗ＋２、０≦ｚ＜２ｗ＋２、であり、ｐ≦ｘ−１、ｙ＋１≦ｑ≦２ｗ＋２、０≦ｒ≦２ｗ＋１である。）

(In the formula (2), w, x, y, z, p, q, r are all integers, 2 ≦ w ≦ 5, 1 ≦ x ≦ 2w + 2, 0 ≦ y <2w + 2, 0 ≦ z <. 2w + 2, p ≦ x−1, y + 1 ≦ q ≦ 2w + 2, 0 ≦ r ≦ 2w + 1.)

  When a raw material composition containing HFO-1233zd (E / Z) and fluorocarbons (A) is brought into contact with a metal catalyst, chlorine atoms and fluorocarbons bonded to carbon atoms constituting HFO-1233zd (E / Z) A fluorine atom bonded to the carbon atom constituting (A) undergoes a halogen exchange reaction by the catalytic action of a metal catalyst, and the chlorine atom of HFO-1233zd (E / Z) is substituted with a fluorine atom. HFO-1234ze Produces. At this time, the E form of HFO-1234ze is selectively generated from the E form and Z form of HFO-1234ze. The production method of the present invention is to produce HFO-1234ze (E) with sufficient conversion and selectivity by using fluorocarbons (A) as a compound to be converted to HFO-1233zd (E / Z). It is possible.

The production method of the present invention may be a continuous production method or a batch production method. The production method of the present invention is preferably a continuous method in terms of production efficiency. In the continuous production method, the reaction site of HFO-1233zd (E / Z), which is a reaction component constituting the raw material composition, and the fluorocarbon (A) (for example, a reactor containing a metal catalyst) is applied. The supply is continuously performed. In the batch production, the above-mentioned reaction components HFO-1233zd (E / Z) and fluorocarbons (A)) may be supplied either earlier or simultaneously. That is, when one of the components of HFO-1233zd (E / Z) and fluorocarbons (A) is supplied, even if the other is not supplied into the reactor, the previously supplied component remains in the reactor. The components to be supplied later may be supplied while staying inside, and HFO-1233zd (E / Z) and fluorocarbons (A) may be brought into contact with the metal catalyst in the reactor for a predetermined time.
Hereinafter, an embodiment in which the method of the present invention is applied to continuous production will be described.

(Raw material composition)
The raw material composition in the present invention contains HFO-1233zd (E / Z) and fluorocarbons (A) as reaction components.

  HFO-1233zd (E / Z) in the present invention may be only HFO-1233zd (E) or HFO-1233zd (Z), and may be HFO-1233zd (E) and HFO-1233zd (Z). ). From the viewpoint of improving reactivity, HFO-1233zd (E / Z) is such that the ratio of HFO-1233zd (E) to the total amount of HFO-1233zd (E / Z) is 50 to 100 mol%, and the rest is HFO-1233zd ( Z) is preferable, and the ratio of HFO-1233zd (E) is more preferably 80 to 100 mol%.

  The fluorocarbons (A) in the present invention are compounds represented by the above formula (1), and are fluorinated hydrocarbons having 2 to 5 carbon atoms. The hydrocarbon group constituting the fluorocarbons (A) may be either a saturated hydrocarbon group or an unsaturated hydrocarbon group, and may be linear, branched or cyclic. Fluorocarbons (A) may be used alone or in combination of two or more. Moreover, as a fluorocarbon (A), the by-product and reaction intermediate produced | generated by reaction of the said Formula (2) can also be used.

  As fluorocarbons (A), w is preferably 2 to 3 in the above formula (1) from the viewpoint of suppressing side reaction products. It is presumed that the fluorine atoms bonded to the carbon atoms of the fluorocarbons (A) are more likely to cause a halogen substitution reaction if they are dispersed to some extent. Therefore, from the viewpoint of improving the reactivity, the number of fluorine atoms bonded to one carbon atom of the fluorocarbons (A) is preferably 1 to 2.

  Specific examples of the fluorocarbons (A) include vinylidene fluoride (VdF), 1,2-dichloro-1,1-difluoroethane (HCFC-132b), 1,1,2-trichloro-2,2-difluoroethane (HCFC). -122), 1-chloro-2,2,2-trifluoroethane (HCFC-133a), dichlorofluoromethane (HCFC-21), chlorodifluoromethane (HCFC-22), trifluoromethane (HFC-23), dichloro Difluoromethane (CFC-12), trichlorofluoromethane (CFC-11), tetrafluoroethylene (TFE), chlorotrifluoroethylene (CTFE), 1,1-dichloro-2,2-difluoroethylene (CFO-1112a), Hexafluoropropene (PFO-1216) etc. It is.

  As fluorocarbons (A), VdF, HCFC-132b, HCFC-122, TFE, CTFE, and CFO-1112a are preferable, and since they have high reactivity with HFO-1233zd (E), HCFC-122, VdF, or HCFC -132b is more preferable.

  Further, the content ratio of HFO-1233zd (E / Z) to the fluorocarbons (A) in the raw material composition is represented by HFO-1233zd (E / Z) / fluorocarbons (A) from the viewpoint of suppressing side reactions. The molar ratio is preferably 1/1 to 5/1. When HFO-1233zd (E / Z) / fluorocarbons (A) is 1/1 or more, generation of side reaction products can be suppressed, and by 5/1 or less, HFO-1233zd (E / Z) can be reduced. It can be produced with sufficient conversion and selectivity. In the present embodiment in which the raw material composition is continuously contacted with the metal catalyst for conversion, the content molar ratio of each component in the raw material composition can be controlled by controlling the flow rate per unit time. .

  In the present invention, the raw material composition can contain other components in addition to HFO-1233zd (E / Z) and fluorocarbons (A), which are reaction components. The total content of HFO-1233zd (E / Z) and fluorocarbons (A) in the raw material composition is 10 mol% or more and 100 mol% or less from the viewpoint of suppressing side reactions and improving the durability of the metal catalyst. Preferably, 30 mol% or more and 70 mol% or less are more preferable, and 30 mol% or more and 50 mol% or less are particularly preferable.

  Other components that can be contained in the raw material composition are not particularly limited, but inert gases such as nitrogen, argon, helium and the like are preferable from the viewpoint of suppressing side reactions and improving the durability of the metal catalyst. . By containing these gases, the reaction components HFO-1233zd (E / Z) and fluorocarbons (A) can be diluted. Hereinafter, these gases are referred to as dilution gases.

  90 mol% or less is preferable with respect to the whole quantity of a raw material composition, the content rate of the dilution gas in a raw material composition has more preferable 30-70 mol%, and 50-70 mol% is especially preferable.

(Metal catalyst)
The metal catalyst is a halogen of a chlorine atom bonded to a carbon atom constituting HFO-1233zd (E / Z) and a fluorine atom bonded to a carbon atom constituting a fluorocarbon (A) in the raw material composition. Has a catalytic effect on the exchange reaction. As a metal catalyst, a metal simple substance, a metal oxide, a metal halide etc. are mentioned, for example. A metal catalyst may be used individually by 1 type, and may use 2 or more types together. Among these, one or more selected from the group consisting of metal oxides and metal halides is preferable because HFO-1233zd (E / Z) can be efficiently converted to HFO-1234ze (E).

Examples of the metal constituting the simple metal, metal oxide, and metal halide include transition metal elements, Group 12 metal elements, and Group 13 metal elements. Among these, Group 6 metal elements, Group 8 metal elements, Group 10 metal elements, Group 12 metal elements, and Group 13 metal elements are preferable, and chromium, iron, zinc, and aluminum are more preferable.
The single metal catalyst may be one of the above metals or an alloy of two or more metals.
The metal oxide catalyst may be one kind of the above-described metal oxide or a composite oxide of two or more kinds of metals.
The metal halide may be a single halide of the above-described metal or a composite halide of two or more metals.

  Specific examples of metal catalysts include iron, cobalt, nickel, palladium, chromium oxide (chromia), aluminum oxide (alumina), zinc oxide, iron fluoride, aluminum fluoride, aluminum chloride, chromium fluoride, chromium chloride, etc. Is mentioned. Among these metal catalysts, one or more selected from the group consisting of aluminum oxide (alumina) and chromium oxide (chromia) in that HFO-1233zd (E / Z) can be efficiently converted to HFO-1234ze (E). Is preferred.

  The metal catalyst may be supported on a carrier. Examples of the carrier include an alumina carrier, a zirconia carrier, a silica carrier, a silica alumina carrier, a carbon carrier represented by activated carbon, a barium sulfate carrier, and a calcium carbonate carrier. Examples of the activated carbon include activated carbon prepared from raw materials such as wood, charcoal, fruit glass, coconut shell, peat, lignite and coal.

  Moreover, it is preferable that the metal catalyst is activated in advance from the viewpoint of improving the reactivity. Examples of the activation treatment method include a method in which the metal catalyst is brought into contact with the activation treatment agent under heating or non-heating. As the activation treatment agent, for example, hydrogen fluoride, hydrogen chloride, fluorine-containing hydrocarbon, or the like can be used. Especially, it is preferable to use a fluorine-containing hydrocarbon as an activation processing agent. As the fluorine-containing hydrocarbon used as the activation treatment agent, for example, CFC-11, HCFC-21, HCFC-22, TFE and the like are suitable.

  In addition to the activation treatment before the reaction, a reactivation treatment can be performed on the metal catalyst. That is, in the conversion reaction, when the activity of the metal catalyst is reduced and the conversion rate of the raw material and the selectivity of the target product, HFO-1234ze (E), are reduced, it is preferable to reactivate the metal catalyst. Thereby, the activity of the metal catalyst can be regenerated and the metal catalyst can be reused. Examples of the reactivation treatment method include a method in which the metal catalyst is brought into contact with the activation treatment agent under heating or non-heating as in the activation treatment before use. As a treatment agent (reactivation treatment agent) for reactivation treatment, oxygen, hydrogen fluoride, hydrogen chloride, a chlorine-containing compound, a fluorine-containing compound, or the like can be used. Examples of the chlorine-containing compound include carbon tetrachloride (R-10), chloroform (R-20), dichloromethane (R-30), vinyl chloride and the like. Examples of the fluorine-containing compound include CFC-11, HCFC-21, HCFC-22, TFE and the like. In the reactivation treatment, an inert gas such as nitrogen, argon, or helium can be used to dilute the reactivation treatment agent from the viewpoint of suppressing side reactions and improving the durability of the metal catalyst.

(Reactor and reaction conditions)
The reactor for reacting HFO-1233zd (E / Z) and fluorocarbons (A) is not particularly limited as long as it can withstand the temperature and pressure in the reactor described later. For example, a cylindrical vertical type A reactor can be used. As a material for the reactor, glass, iron, nickel, iron, an alloy containing nickel as a main component, or the like is used. Further, the reactor may be provided with an electric heater for heating the inside of the reactor.

  A metal catalyst is accommodated in such a reactor, and a reaction part is formed. The metal catalyst may be accommodated in either a fixed bed type or a fluidized bed type. In the case of a fixed bed type, either a horizontal fixed bed type or a vertical fixed bed type may be used, but in a mixed gas composed of multiple components, the concentration distribution of each component varies depending on the location due to the difference in specific gravity. The vertical fixed floor type is preferable because it is easy to prevent the occurrence.

  The metal catalyst in the reactor may be activated before being accommodated in the reactor, but since the operation is simple and the work efficiency is high, the activation treatment is performed in the state accommodated in the reactor. It is preferable. Therefore, it is preferable to perform the activation treatment by introducing the activation treatment agent into the reactor containing the metal catalyst. The activation treatment agent may be introduced into the reactor at room temperature, but from the viewpoint of improving reactivity, it is preferable to adjust the temperature by heating or the like when introduced into the reactor.

  In order to increase the efficiency of the treatment, it is preferable to carry out the activation treatment while the inside of the reactor is heated. In that case, the temperature in the reactor is preferably 200 to 400 ° C.

  The reaction components HFO-1233zd (E / Z) and fluorocarbons (A) may be introduced into the reactor at room temperature, but in order to improve the reactivity in the reactor, It is preferable to supply after heating (preheating) before introduction. When preheating is performed, it is preferable that HFO-1233zd (E / Z) is heated to a temperature of 80 to 150 ° C. and then supplied to the reactor. The fluorocarbons (A) are preferably supplied to the reactor after being heated to a temperature of 80 to 150 ° C. These preheating may be performed in a lump after mixing HFO-1233zd (E / Z) and fluorocarbons (A), or separately preheating, further mixing, and then heating the mixture to a predetermined temperature. For example, the temperature may be adjusted in two steps to a desired temperature.

In the embodiment of the present invention, the conversion reaction of HFO-1233zd (E / Z) to HFO-1233ze (E) may be performed in the liquid phase or in the gas phase. It is preferable to carry out in the gas phase because the produced HFO-1234ze (E) can be easily desorbed from the catalyst surface and the product concentration on the catalyst surface can be lowered. When reacting in the gas phase, it is preferable to heat HFO-1233zd (E / Z), which is liquid at room temperature, to the above-mentioned preferable temperature, vaporize it, and introduce it into the reactor. In addition, among the fluorocarbons (A) as reaction components, those that are liquid at room temperature, such as HCFC-132b, HCFC-122, HCFC-133a, CFC-11, CFO-1112a, are heated to the above preferred temperatures. It is preferable to vaporize and introduce into the reactor.
Hereinafter, the case where the reaction of R-20 and / or R-30 with the fluorocarbons (A) is carried out in the gas phase will be described.

  As described above, the raw material composition contains a diluent gas together with HFO-1233zd (E / Z) and fluorocarbons (A), which are reaction components, from the viewpoint of suppressing side reactions and improving the durability of the metal catalyst. It is preferably contained. In the case of a gas phase reaction, such mixing of the dilution gas is preferable from the viewpoint of easy supply of the raw material composition to the reactor and adjustment of the flow rate.

  From the point of improving the reactivity, the raw material composition containing the diluent gas and the reaction component is preferably introduced into the reactor after having a temperature of 80 to 150 ° C. as described above. The reaction component and the dilution gas may be mixed after preheating to the above temperature, and the mixed raw material composition at the above temperature may be supplied to the reactor, or the raw material composition may be mixed first to obtain the raw material composition. The composition may be heated to the above temperature and fed to the reactor.

  The HFO-1233zd (E / Z) and fluorocarbons (A), which are the reaction components, and the supply of the diluent gas used as necessary to the reactor may be separate or each component may be mixed. You may supply from. In addition, when supplying HFO-1233zd (E / Z) and fluorocarbons (A) which are reaction components and further diluting gas used as necessary, the raw material composition is divided into groups, For example, it may be divided into components that are gases at normal temperature and other components, and each component may be mixed in each group and supplied separately to the reactor, or all components may be mixed and then supplied.

  In this way, the HFO-1233zd (E / Z) and the fluorocarbons (A) introduced into the reactor are brought into contact with the metal catalyst in the reactor. At this time, from the point of improving the reactivity, the temperature condition is preferably 50 to 400 ° C., more preferably 150 to 350 ° C. as the temperature in the reactor, and the pressure condition is 0 to 2 MPa as the pressure in the reactor. Gauge pressure is preferred. The contact time between the raw material composition and the metal catalyst in the reactor is preferably 0.1 to 500 seconds, more preferably 1 to 50 seconds.

(Reactor)
In the present invention, an example of a reaction apparatus used for production of HFO-1234ze (E) is shown in FIG. A reaction apparatus 1 shown in FIG. 1 includes a reactor 2 including heating means such as an electric heater. In addition, installation of the heating means in the reactor 2 is not essential.

  A metal catalyst 3 is accommodated in the reactor 2. The reactor 2 is connected to a preheating mixer 4 having heating means such as an electric heater. The preheating mixer 4 is connected to the reactor 2 by a raw material supply line 5. The raw material composition consisting of HFO-1233zd (E / Z), fluorocarbons (A) and diluent gas as reaction components is mixed in the preheating mixer 4 and then supplied to the reactor 2 in a gaseous state. The preheating mixer 4 includes a first supply line 6 for supplying a compound that is liquid at normal temperature among the raw material components, a second supply line 7 for supplying a compound that is gas at normal temperature among the raw material components, and an activation treatment. It is preferable that the 2nd supply line 8 which supplies an agent, and the dilution gas supply line 9 which supplies dilution gas are connected.

  The first supply line 6 is provided with a preheater (preheater) 6a equipped with an electric heater or the like, and the preheated mixer after the supplied HFO-1233zd (E / Z) is preheated to a predetermined temperature. 4 is supplied. The predetermined temperature is preferably a temperature equal to or higher than the boiling point of the liquid raw material component. That is, it is preferable that the liquid raw material component is supplied to the preheating mixer 4 after being preheated and in a gaseous state. In addition, a preheater (not shown) equipped with an electric heater or the like is installed in the second supply line, the activation treatment agent supply line, and the dilution gas supply line, and the gas raw material supplied through that line. Ingredients, activation agents or diluent gases may be preheated to a predetermined temperature. In addition, installation of the preheater (preheater) 6a in the 1st supply line 6 is not essential.

  An outlet line 11 in which a cooling means 10 such as a heat exchanger is installed is connected to the outlet of the reactor 2. In the outlet line 11, a steam and acidic liquid recovery tank 12, an alkali cleaning device 13 and a dehydration tower 14 are further installed in this order. Then, after dehydration by the dehydration tower 14, each component of the outlet gas is preferably analyzed and quantified by an analyzer such as gas chromatography (GC).

(Outlet gas component)
In the production method of the present invention, HFO-1234ze (E) can be obtained as a component of the outlet gas from the reactor 2. As fluorocarbons (A), VdF, HCFC-132b, HCFC-122, HCFC-133a, HCFC-21, HCFC-22, HFC-23, CFC-12, CFC-11, TFE, CTFE, CFO-1112a, PFO When -1216 or the like is used, the reaction product HFO-1234ze (E), the unreacted reaction component HFO-1233zd (E / Z), and the fluorocarbons (A) are used as outlet gas components. In addition, HFC-143a, HCFO-1131a, vinylidene chloride (VdCl), 1-chloro-2,2-difluoroethylene (HCFO-1122), 1,2-dichloro-1-fluoroethylene (HCFO-1121), trichloroethylene Tetrachloroethylene, 3-chloro-1,3,3-tri Ruoropuropen (HFO-1233ze) and the like can be obtained. Among the components contained in these outlet gases, HFO-1234ze (E), HFO-1234ze (Z), HFO-1233ze, and the like are compounds derived from the reaction component HFO-1233zd (E / Z), HFC-143a, HCFO-1131a, VdCl, HCFO-1122, HCFO-1221, trichlorethylene, tetrachloroethylene, and the like are compounds derived from the fluorocarbons (A) as a reaction component.

  These reaction products obtained as the outlet gas component can be used for various purposes as they are, but it is preferable to increase the purity of HFO-1234ze (E). The above components other than HFO-1234ze (E) contained in the outlet gas may be separated by known means such as distillation, adsorption, washing with an acidic aqueous solution, basic aqueous solution or neutral aqueous solution, and removed to the desired extent. it can. Especially, highly purified HFO-1234ze (E) can be obtained by distilling under a normal pressure, pressurization, or pressure reduction.

(Use of HFO-1234ze (E))
HFO-1234ze (E) is a refrigerant, a foaming agent, a cleaning agent, a solvent and an aerosol in place of HFO-134a, HFO-152a and HFO-245fa, which are greenhouse gases, and a raw material monomer of a functional material, and for synthesis Useful as an intermediate.

  According to the production method of the present invention, HFO-1233zd (E / Z) and fluorocarbons (A) are used as raw materials, and it is useful as a new refrigerant having a low global warming potential (GWP) without reacting with hydrogen fluoride. HFO-1234ze (E) can be produced. Therefore, the production method of the present invention reduces the cost required for the production facility and the labor for safety risk management, compared with, for example, a method in which HFO-1233zd (E / Z) is reacted with hydrogen fluoride directly in the presence of a catalyst. can do.

  Next, the present invention will be described in more detail using examples. The present invention is not limited to the following examples.

(Analysis conditions)
A gas chromatogram (GC) was used for composition analysis. DB-1301 (length 60 m × inner diameter 250 μm × thickness 1 μm, manufactured by Agilent Technologies) was used as the column.

(Reactors used in catalyst activation examples 1 and 2 and examples 1 to 14)
As the reaction apparatus, the same reaction apparatus as shown in FIG. 1 was used. A vertical fixed bed reactor made of stainless steel (SUS316) having an inner diameter of 14 mm and a height of 400 mm was used as the reactor. An insertion tube made of SUS316 having a diameter of 3.1 mm was introduced into the center of the reactor, and a K-type thermocouple was inserted therein to measure the internal temperature. In the center of the reactor, the metal catalyst prepared in Catalyst Activation Example 1 or Catalyst Activation Example 2 was packed at a height of 150 mm. The reactor was heated by an electric furnace. A preheating mixer connected to the first supply line and the second supply line was connected to the upper part of the reactor, and the first supply line and the preheating mixer were each heated to 100 ° C. by an electric furnace. HCFC-22 used as an activation treatment agent, VdF and nitrogen used in Examples 1 to 5, and 10 were supplied to the preheating mixer from the second supply line after adjusting the gas flow rate with a mass flow controller. In addition, HFO-1233zd (E) and HCFC-132b used in Examples 6-9 and 11-14, the liquid flow rate was adjusted using a plunger pump and heated to 100 ° C. with a preheater (preheater). After vaporization, the mixture was supplied to the preheating mixer through the first supply line. The reaction product was continuously taken out from the sample line branched and connected to the outlet line at the bottom of the reactor, and analyzed using the gas chromatogram (GC) described above. Note that the preheating temperature, reaction temperature, and pressure conditions of HCFC-22 used for activation of HFO-1233zd (E), VdF, nitrogen, and catalyst are actually measured values in the reactor.

(Catalyst preparation example 1: chromia catalyst preparation)
1,100 g of Cr (NO ₃ ) ₃ · 9H ₂ O and 150 g of Mg (NO ₃ ) ₂ · 6H ₂ O were dissolved in 2.5 liters of water, and 2000 g of 28% aqueous ammonium hydroxide solution was added. . This was added to 4 liters of heated water with stirring to obtain a hydroxide precipitate. Next, the precipitate was separated by filtration, washed with pure water and dried, and then calcined at 420 ° C. for 5 hours to obtain an oxide powder. The obtained oxide powder was molded into a cylindrical shape having a diameter of 5 mm and a height of 5 mm with a tableting machine to prepare a chromia catalyst.

(Catalyst activation example 1: activation of alumina catalyst)
The reactor was filled with 20 g of an alumina catalyst (Al ₂ O ₃ , manufactured by Catalyst Kasei Co., Ltd., trade name: ACBM-1, shape: particle size 2 mm spherical) and dried at 300 ° C. for 10 hours while flowing nitrogen gas at 100 sccm. did. Then, after mixing HCFC-22 at a rate of 1.37 mmol / min and nitrogen gas at a rate of 2.74 mmol / min, the mixture was supplied to the reactor. The reaction was carried out at a reaction temperature of 300 ° C., and after 11 hours, it was confirmed that the outlet gas composition had stabilized, and the activation was completed.

(Catalyst activation example 2: Activation of chromia catalyst)
The reactor was filled with 29 g of the chromia catalyst prepared in Catalyst Preparation Example 1, and dried at 300 ° C. for 10 hours under a flow of nitrogen gas at 100 sccm. Thereafter, HCFC-22 was mixed at 1.37 mmol / min and nitrogen gas was mixed at 2.74 mmol / min, and then supplied to the reactor. The reaction was carried out at a reaction temperature of 300 ° C., and after 7.5 hours, it was confirmed that the outlet gas composition had stabilized, and the activation was completed.

(Example 1: Reaction 1 of a composition containing HFO-1233zd (E) and VdF over an activated alumina catalyst)
The temperature of the reactor charged with the catalyst prepared in Catalyst Activation Example 1 was 250 ° C., and HFO-1233zd (E) (HFO-1233zd (E) = 97.7 mol%, HFO-1233ze = 2.3 mol%. ) At 1.12 mmol / min, VdF at 1.12 mmol / min, and nitrogen at 2.25 mmol / min, and then fed to the reactor. The reaction was continued, and after 5.5 hours, it was confirmed that the outlet gas composition had stabilized, and the reaction was completed. The gas chromatogram analysis composition of the outlet gas at 5.5 hours is shown in Table 1.

(Examples 2 to 5: Reactions 2 to 5 of a composition containing HFO-1233zd (E) and VdF with an activated alumina catalyst)
The reaction was performed in the same manner as in Example 1 except that the reaction conditions were changed to those described in Table 1. The results are shown in Table 1.

Example 6 Reaction 1 of Composition Containing HFO-1233zd (E) and HCFC-132b with Activated Alumina Catalyst
The catalyst prepared in Catalyst Activation Example 1 was charged into the reactor, and the reactor temperature was 250 ° C., and HFO-1233zd (E) (HFO-1233zd (E) = 97.7 mol%, HFO-1233ze = 2. 3 mol%) was mixed at 1.12 mmol / min, HCFC-132b at 1.12 mmol / min, and nitrogen at 2.25 mmol / min, and then fed to the reactor. The reaction was continued, and after 21 hours, it was confirmed that the outlet gas composition had stabilized, and the reaction was completed. The gas chromatogram analysis composition of the outlet gas at 21 hours is shown in Table 1 as a ratio with respect to the entire compounds other than nitrogen.

(Examples 7 to 9: Reactions 2 to 4 of a composition containing HFO-1233zd (E) and HCFC-132b with activated alumina catalyst)
The reaction was performed in the same manner as in Example 6 except that the reaction conditions were changed to those described in Table 1. The results are shown in Table 1.

(Example 10: Reaction of composition containing HFO-1233zd (E) and VdF by activated chromia catalyst)
The catalyst prepared in Catalyst Activation Example 2 was charged into the reactor, the reactor temperature was 250 ° C., and HFO-1233zd (E) (HFO-1233zd (E) = 97.7 mol%, HFO-1233ze = 2. 3 mol%) was mixed at 1.12 mmol / min, VdF at 0.56 mmol / min, and nitrogen at 2.81 mmol / min, and then fed to the reactor. The reaction was continued in the reactor, and after 22.5 hours, it was confirmed that the outlet gas composition had stabilized, and the reaction was completed. The gas chromatogram analysis composition of the outlet gas at 22.5 hours is shown in Table 2.

(Example 11: Reaction 1 of composition containing HFO-1233zd (E) and HCFC-132b by activated chromia catalyst)
The catalyst prepared in Catalyst Activation Example 2 was charged into the reactor, the reactor temperature was 250 ° C., and HFO-1233zd (E) (HFO-1233zd (E) = 97.7 mol%, HFO-1233ze = 2. 3 mol%) was mixed at 1.12 mmol / min, HCFC-132b at 1.12 mmol / min, and nitrogen at 2.25 mmol / min, and then fed to the reactor. The reaction was continued in the reactor, and after 21 hours, it was confirmed that the outlet gas composition had stabilized, and the reaction was completed. The gas chromatogram analysis composition of the outlet gas at 21 hours is shown in Table 2.

(Examples 12 to 14: Reaction 2 to 4 of a composition containing HFO-1233zd (E) and HCFC-132b by an activated chromia catalyst)
The reaction was performed in the same manner as in Example 11 except that the reaction conditions were changed to those described in Table 2. The results are shown in Table 2.

  Further, based on the molar composition of the outlet gas obtained by analysis by gas chromatography, the yield and conversion rate (reaction rate) of HFO-1233zd (E), the yield and conversion rate (reaction rate) of VdF, The yield and conversion rate (reaction rate) of HCFC-132b were determined as follows. These results are shown in the lower column of Table 1.

[HFO-1233zd (E) conversion rate (mol%)]
The ratio of components other than HFO-1233zd (E) among the components derived from HFO-1233zd (E) in the outlet gas. (HFO-1234ze (E) + HFO-1234ze (Z) + HFO-1233zd (Z) + HFO-1233ze) / (HFO-1233zd (E) + HFO-1234ze (E) + HFO-1234ze (Z) + HFO-1233zd) in the outlet gas (Z) + HFO-1233ze) × 100 (mol%))

[VdF conversion (mol%)]
The ratio of components other than VdF among the components derived from VdF in the outlet gas. Calculated by (HFO-143a + HCFO-1131a) / (VdF + HFC-143a + HCFO-1131a) × 100 (mol%) in the outlet gas.

[HCFC-132b conversion (mol%)]
The ratio of components other than HCFC-132b among the components derived from HCFC-132b in the outlet gas. It is calculated by (HCFC-133a + HCFO-1121 + HCO-1120) / (HCFC-132b + HCFC-133a + HCFO-1121 + HCO-1120) × 100 (mol%) in the outlet gas.

[HFO-1234ze (E) selectivity (mol%)]
Of the reacted HFO-1233zd (E), the percentage converted to HFO-1234ze (E) means. HFO-1234ze (E) / (HFO-1234ze (E) + HFO-1234ze (Z) + HFO-1233zd (Z) + HFO-1233ze) × 100 (mol%) in the outlet gas.

  As described above, according to the present example, HFO-1233zd (E / Z) and fluorocarbons (A) are used as raw materials, and hydrogen fluoride is not used as a raw material. As a new refrigerant having a low global warming potential (GWP). Useful HFO-1234ze (E) can be produced. Therefore, the production method of the present invention reduces the cost required for the production facility and the labor for safety risk management, compared with, for example, a method in which HFO-1233zd (E / Z) is reacted with hydrogen fluoride directly in the presence of a catalyst. can do.

  The method for producing HFO-1234ze (E) of the present invention is a novel production method and can be suitably used for producing HFO-1234ze (E).

  DESCRIPTION OF SYMBOLS 1 ... Reaction apparatus, 2 ... Reactor, 3 ... Metal catalyst, 4 ... Preheating mixer, 5 ... Raw material supply line, 6 ... 1st supply line, 6a ... Preheater (preheater), 7 ... 2nd supply Line, 8 ... Activation treatment agent supply line, 9 ... Dilution gas supply line, 10 ... Cooling means, 11 ... Outlet line, 12 ... Acidic liquid recovery tank, 13 ... Alkaline washing apparatus, 14 ... Dehydration tower

Claims (6)

((E) and / or (Z))-1-chloro-3,3,3-trifluoropropene and ((E) and / or (Z))-1-chloro represented by the following general formula (1) Contacting a raw material composition containing at least one fluorocarbon other than -3,3,3-trifluoropropene with a metal catalyst;
The ((E) and / or (Z))-1-chloro-3,3,3-trifluoropropene is converted to (E) -1,3,3,3-tetrafluoropropene. (E) A method for producing 1,3,3,3-tetrafluoropropene.

(In the formula (1), w, x, y, and z are all integers, and 2 ≦ w ≦ 5, 1 ≦ x ≦ 2w + 2, 0 ≦ y <2w + 2, and 0 ≦ z <2w + 2)   The method for producing (E) -1,3,3,3-tetrafluoropropene according to claim 1, wherein the metal catalyst is at least one selected from the group consisting of a simple metal, a metal oxide and a metal halide. .   The (E) -1,3,3,3-tetrafluoropropene according to claim 1 or 2, wherein the metal catalyst is at least one selected from the group consisting of chromium oxide (chromia) and aluminum oxide (alumina). Manufacturing method.   The method for producing (E) -1,3,3,3-tetrafluoropropene according to any one of claims 1 to 3, wherein the raw material composition and the metal catalyst are contacted in a gas phase.   Fluorocarbons other than ((E) and / or (Z))-1-chloro-3,3,3-trifluoropropene represented by the general formula (1) are 1,1,2-trichloro-2,2- The (E) -1,3 according to any one of claims 1 to 4, which is at least one selected from the group consisting of difluoroethane, 1,1-difluoroethylene and 1,2-dichloro-1,1-difluoroethane. , 3,3-Tetrafluoropropene production method.   The method for producing (E) -1,3,3,3-tetrafluoropropene according to any one of claims 1 to 5, wherein a temperature at which the raw material composition is brought into contact with a metal catalyst is 50 to 400 ° C.

Images