WO2018092780A1 - Method for producing 1-chloro-2, 3, 3-trifluoropropene - Google Patents

Abstract

Provided is a method for producing 1-chloro-2, 3, 3-trifluoropropene, which efficiently produces 1-chloro-2, 3, 3-trifluoropropene by efficiently removing one or more compounds selected from among water, 1-chloro-3, 3-difluoro-1-propyne, oxides and HCFC-244ca from a composition that contains 1-chloro-2, 3, 3-trifluoropropene. A method for producing 1-chloro-2, 3, 3-trifluoropropene, wherein a composition that contains 1-chloro-2, 3, 3-trifluoropropene and at least one compound selected from among water, 1-chloro-3, 3-difluoro-1-propyne, oxides and 3-chloro-1, 1, 2, 2-tetrafluoropropane is brought into contact with a solid adsorbent, thereby removing the compound contained in the composition.

Description

Process for producing 1-chloro-2,3,3-trifluoropropene

The present invention relates to 1-chloro-2,3,3-trifluoropropene, water, 1-chloro-3,3-difluoro-1-propyne, oxide and 3-chloro-1,1,2,2-tetra 1-chloro-2,3,3-trifluoropropene for removing impurities other than 1-chloro-2,3,3-trifluoropropene in a composition comprising one or more compounds selected from fluoropropane It relates to the manufacturing method.

Hydrochlorofluorocarbon (HCFC) has an adverse effect on the ozone layer, so its production is scheduled to be regulated. HCFC is, for example, 3,3-dichloro-1,1,1,2,2-pentafluoropropane (HCFC-225ca) and 1,3-dichloro-1,1,2,2,3-pentafluoropropane ( HCFC-225cb) and the like, but with the HCFC regulations, development of a compound that replaces the HCFC is desired.

An example of a compound that replaces HCFC is 1-chloro-2,3,3-trifluoropropene (HClC = CF—CHF _2, HCFO-1233yd). 1233yd has a low global warming potential (GWP) and is a useful compound for use in cleaning agents, solvents, refrigerants, blowing agents and aerosols.

Here, in Patent Document 1, 3-chloro-1,1,2,2-tetrafluoropropane (HCFC-244ca) is reacted with hydrogen fluoride in a gas phase in a nitrogen stream using chromium hydroxide as a catalyst. Thus, a method for producing 1,1,2,2,3-pentafluoropropane (HCFC-245ca) is disclosed. In this method, 1233yd is by-produced. Therefore, a composition containing 1233yd can be obtained by recovering the composition obtained by the above reaction and separating 1233yd contained in the composition. The composition containing 1233yd obtained in this way can be used for cleaning agents, solvents, refrigerants, blowing agents or aerosol applications.

By the way, the composition containing 1233yd obtained by the above production method includes HCFC-244ca which is an unreacted raw material, 1-chloro-3,3-difluoro-1-propyne by-produced in the production process, water, in air Oxide produced by oxidation of 1233yd with oxygen of oxygen may be included.

When the composition containing 1233yd is used as a cleaning agent, solvent, refrigerant, blowing agent or aerosol, the composition containing 1233yd contains high-concentration water, 1-chloro-3,3-difluoro-1-propyne, HCFC. Including -244ca and the like may cause various reliability and performance problems. In order to reduce such undesirable effects, it is preferable to reduce the amount of water, 1-chloro-3,3-difluoro-1-propyne, HCFC-244ca and the like contained in the composition containing 1233yd as much as possible. .

Further, when a composition containing 1233yd is used as a cleaning agent, solvent, refrigerant, foaming agent or aerosol, if the composition containing 1233yd contains a high concentration of oxide, the stability is lowered and the generation of an acidifying substance is caused. May cause problems. In order to suppress such undesirable effects, it is preferable to reduce the amount of oxide mixed in the composition containing 1233yd as much as possible.

However, Patent Document 1 does not describe a method for efficiently removing water, 1-chloro-3,3-difluoro-1-propyne and oxide from a composition containing 1233yd.

International Publication No. 1994/014737

The present invention has been made from the above viewpoint, and comprises 1233yd and one or more compounds selected from water, 1-chloro-3,3-difluoro-1-propyne, oxide and HCFC-244ca An object of the present invention is to provide a process for producing 1233yd that can efficiently remove one or more compounds selected from water, 1-chloro-3,3-difluoro-1-propyne, oxide and HCFC-244ca.

The method for producing 1-chloro-2,3,3-trifluoropropene (HCFO-1233yd, hereinafter simply referred to as “1233yd”) of the present invention includes 1-chloro-2,3,3-trifluoropropene and A composition comprising: water, 1-chloro-3,3-difluoro-1-propyne, oxide and 3-chloro-1,1,2,2-tetrafluoropropane Contacting with an adsorbent removes the compound contained in the composition.

In the method for producing 1-chloro-2,3,3-trifluoropropene of the present invention, the solid adsorbent preferably contains at least one selected from activated carbon, zeolite, silica and alumina.

In the method for producing 1-chloro-2,3,3-trifluoropropene of the present invention, the composition contains water, the solid adsorbent contains at least one selected from zeolite, silica and alumina, and the composition It is preferable to remove the water from the product.

In the method for producing 1-chloro-2,3,3-trifluoropropene of the present invention, the composition contains an oxide, the solid adsorbent contains at least one selected from activated carbon and alumina, and the composition It is preferable to remove the oxide from the product.

In the method for producing 1-chloro-2,3,3-trifluoropropene according to the present invention, the oxide may be 3-chloro-2- (difluoromethyl) -2-fluorooxirane, 2,2-difluoroacetylfluorine. , Formyl chloride, E form of 1-chloro-2,3,3-trifluoro-1-hydroperoxy-1-propene, 1-chloro-2,3,3-trifluoro-1-hydroperoxy- Z form of 1-propene, 3-chloro-1,1,2-trifluoro-3-hydroperoxy-1-propene, 1-chloro-2,3,3-trifluoro-3-hydroperoxy-1 -At least one selected from E form of propene and Z form of 1-chloro-2,3,3-trifluoro-3-hydroperoxy-1-propene.

In the method for producing 1-chloro-2,3,3-trifluoropropene according to the present invention, the composition contains 1-chloro-3,3-difluoro-1-propyne, and the solid adsorbent is activated carbon. It is preferable to include at least one selected from silica and alumina and remove the 1-chloro-3,3-difluoro-1-propyne from the composition.

In the method for producing 1-chloro-2,3,3-trifluoropropene of the present invention, the composition contains 3-chloro-1,1,2,2-tetrafluoropropane, and the solid adsorbent is It is preferable to include at least one selected from activated carbon, alumina, zeolite 4A and zeolite 5A, and remove the 3-chloro-1,1,2,2-tetrafluoropropane from the composition.

The method for producing 1-chloro-2,3,3-trifluoropropene of the present invention comprises 1-chloro-2,3,3-trifluoropropene and 3-chloro-1,1,2,2-tetrafluoro. At least one compound selected from water, 1-chloro-3,3-difluoro-1-propyne, oxide and 3-chloro-1,1,2,2-tetrafluoropropane by dehydrofluorinating propane And a step of producing a composition comprising:

According to the production method of the present invention, from a composition comprising 1233yd and one or more compounds selected from water, 1-chloro-3,3-difluoro-1-propyne, oxide and HCFC-244ca, water, One or more compounds selected from 1-chloro-3,3-difluoro-1-propyne, oxide and HCFC-244ca can be efficiently removed.
Moreover, according to the manufacturing method of this invention, 1233yd with high purity can be manufactured efficiently.

Embodiments of the present invention will be described below.
<First Embodiment>
The process for producing 1233yd according to the first embodiment of the present invention comprises 1233yd and one or more compounds selected from water, 1-chloro-3,3-difluoro-1-propyne, oxide and HCFC-244ca. In the method for producing 1233yd, the composition comprising the above is brought into contact with a solid adsorbent to remove one or more compounds selected from water, 1-chloro-3,3-difluoro-1-propyne, oxide and HCFC-244ca. is there. Hereinafter, “one or more compounds selected from water, 1-chloro-3,3-difluoro-1-propyne, oxide and HCFC-244ca” is also referred to as “impurity (A)”, and 1233yd and impurity (A) are The composition containing the composition is also referred to as “purification composition”. By bringing the purification composition into contact with the solid adsorbent, the impurity (A) is removed from the purification composition, 1233yd is purified, and high-purity 1233yd can be produced. Here, as for the removal of the impurity (A), a part thereof may be removed or the whole may be removed.

[Purification composition]
The composition for purification in the present embodiment is not particularly limited as long as it is a composition containing 1233yd and impurities (A). Moreover, the composition for refinement | purification may contain other components other than 1233yd and an impurity (A). Other components are by-products generated in the manufacturing process of 1233yd. The composition for purification may be liquid or gas.

As the composition for purification in the present embodiment, for example, a reaction product containing 1233yd obtained by reacting various raw material components for the purpose of producing 1233yd can be used. That is, as will be described later, when 1233yd and impurities (A) are contained in the reaction product in the production step of 1233yd, this reaction product can be used as it is as a purification composition. In addition, a composition obtained by washing the reaction product with water or alkali to remove acidic substances such as hydrogen fluoride and hydrogen chloride contained in the reaction product can be used as a purification composition.

In the production method of the present embodiment, specifically, the purification composition to be brought into contact with the solid adsorbent includes a reaction product containing 1233yd obtained by the following method (I) or (II).
(I) A method of reacting HCFC-244ca with hydrogen fluoride in the gas phase in a nitrogen stream using chromium oxide as a catalyst. (II) HCFC-244ca using potassium hydroxide or sodium hydroxide as a reactant at 40 ° C. to 80 ° C. Dehydrofluorination reaction at a temperature of ℃

(1233yd)
Since 1233yd is a fluoroolefin having a double bond between carbon atoms, the lifetime in the atmosphere is short, and the ozone depletion coefficient and the global warming coefficient are small.

1233yd has a Z isomer and an E isomer, which are geometric isomers, depending on the position of the substituent on the double bond. In the present specification, when a compound name or an abbreviation of a compound is used without particular notice, it indicates any of Z-form, E-form, and a mixture of Z-form and E-form. When (E) or (Z) is appended, it indicates that the compound is an E-form or a Z-form. For example, 1233yd (Z) indicates a Z body, and 1233yd (E) indicates an E body.

1233yd (Z) has a boiling point of about 54 ° C., and 1233yd (E) has a boiling point of about 48 ° C., both of which are excellent in drying properties. Moreover, even if it is boiled to become steam, the temperature of the steam is near the boiling point of each, so that it is difficult to adversely affect resin parts and the like that are easily affected by heat. Further, 1233yd has no flash point, low surface tension and viscosity, and has excellent performance as a cleaning solvent and coating solvent, such as being easily evaporated at room temperature.

Although the composition for purification in the present embodiment only needs to contain a small amount of 1233yd, the content of 1233yd is preferably 5% by mass or more with respect to the total amount of the composition for purification, and is 10% by mass or more. More preferably, it is more preferably 50% by mass or more, particularly preferably 70% by mass or more, and most preferably 80% by mass or more. If content of 1233yd is more than the said lower limit, the removal efficiency of an impurity (A) will be good. The content of 1233yd and impurity (A) in the purification composition in the present embodiment is not particularly limited, but in terms of removal efficiency of impurity (A), the mole represented by (impurity (A)) / (1233yd) The ratio is preferably less than 1, more preferably 0.001 to 0.7, and still more preferably 0.1 to 0.2.

(water)
The composition for purification in the present embodiment includes, for example, water produced in the production process of 1233yd and water mixed when the reaction product obtained in the production process of 1233yd is washed with water or alkali. There is. When the composition for purification contains water, the content of water in the composition for purification is preferably 1% by mass or less based on the total amount of the composition for purification from the viewpoint of the removal efficiency of impurities (A). 0.5 mass% or less is more preferable, and 0.1 mass% or less is further more preferable.

(1-Chloro-3,3-difluoro-1-propyne)
The purification composition may contain 1-chloro-3,3-difluoro-1-propyne by-produced in the production process of 1233yd. 1-Chloro-3,3-difluoro-1-propyne is produced by the progress of a 1233yd dehydrofluorination reaction represented by the following formula [1].
CHCl = CFCHF ₂ → CCl≡CCHF ₂ + HF (1)

When the composition for purification contains 1-chloro-3,3-difluoro-1-propyne, the content of 1-chloro-3,3-difluoro-1-propyne in the composition for purification is the amount of impurities (A) In terms of removal efficiency, it is preferably 1% by mass or less, more preferably 0.5% by mass or less, and still more preferably 0.1% by mass or less with respect to the total amount of the purification composition.

(oxide)
The composition for purification in the present embodiment may contain oxide.
Oxide is an oxide produced by reaction of 1233yd with oxygen. Specifically, 3-chloro-2- (difluoromethyl) -2-fluorooxirane (chemical formula (A)), 2,2-difluoroacetyl fluoride (chemical formula (B), formyl chloride (chemical formula (C)), (E, Z) -1-chloro-2,3,3-trifluoro-1-hydroperoxy-1-propene (chemical formula (D)), 3-chloro-1,1,2-trifluoro-3- Hydroperoxy-1-propene (chemical formula (E)), (E, Z) -1-chloro-2,3,3-trifluoro-3-hydroperoxy-1-propene (chemical formula (F)), etc. Can be mentioned.

3-Chloro-2- (difluoromethyl) -2-fluorooxirane, 2,2-difluoroacetyl fluoride, and formyl chloride can be quantified by analysis using gas chromatography. (E, Z) -1-chloro-2,3,3-trifluoro-1-hydroperoxy-1-propene, 3-chloro-1,1,2-trifluoro-3-hydroperoxy-1- Proper, hydroperoxides having an -OOH structure such as (E, Z) -1-chloro-2,3,3-trifluoro-3-hydroperoxy-1-propene are quantified by the following reaction formula [2] As shown in [3], it is carried out by titration with sodium iodide and back titration with sodium thiosulfate. ROOH represents any hydroperoxide.

ROOH + 2NaI + H ₂ O → I ₂ + 2NaOH + ROH
... [2]
I ₂ + 2Na ₂ S ₂ O ₃ → Na ₂ S ₄ O ₆ + 2NaI [3]

Specifically, the titration and the back titration are performed as follows. About 50 mL of a sample solution containing hydroperoxide (ROOH) is mixed with 2.5% by mass of sodium iodide (NaI) and about 40 mL of acetone solution, and further mixed with about 50 mL of cold water. The mixture is colored yellow with iodine (I ₂ ) generated as represented in [2]. In this case, when coloring does not occur, it is determined that the hydroperoxide is below the detection lower limit. When colored, the mixture is back titrated with 0.01 mol / L (0.01 N) aqueous sodium thiosulfate (Na ₂ S ₂ O ₃ ) until the color disappears. The quantitative value of hydroperoxide is determined by the following formula using the titration experimental value.

Hydroperoxide [mass ppm]
= {Na ₂ S ₂ O ₃ aqueous solution consumption [mL] x Na ₂ S ₂ O ₃ molarity [mol / mL] x (1/2) x ROOH molecular weight} / sample solution weight [g] x 10 ⁶

When the composition for purification contains oxide, the content of oxide in the composition for purification is preferably 0.1% by mass or less with respect to the composition for purification in terms of the removal efficiency of impurities (A). 05 mass% or less is more preferable, and 0.01 mass% or less is further more preferable.

(HCFC-244ca)
HCFC-244ca is used as a raw material for producing 1233yd, for example. In this case, HCFC-244ca is contained in the purification composition as an unreacted raw material. When the purification composition contains HCFC-244ca, the content of HCFC-244ca in the purification composition is preferably 1% by mass or less, and 0.5% by mass or less in terms of the removal efficiency of impurities (A). More preferred is 0.1% by mass or less.

[Solid adsorbent]
The solid adsorbent in this embodiment adsorbs one or more compounds selected from water, 1-chloro-3,3-difluoro-1-propyne, oxide and HCFC-244ca. Examples of the solid adsorbent include activated carbon, zeolite, silica, alumina and the like. One solid adsorbent may be used alone, or two or more solid adsorbents may be used in combination.

The solid adsorbent is preferably one that has been previously heat-treated with a dry gas at 100 ° C. to 400 ° C. or heat-treated under reduced pressure before being brought into contact with the purification composition. Thereby, the adsorption | suction performance of an impurity (A) can be improved.

(Activated carbon)
The activated carbon used in the present embodiment is, for example, wood, wood powder, coconut shell, by-product during pulp production, bacus, waste molasses, peat, lignite, lignite, bituminous coal, anthracite, petroleum distillation residue components, petroleum pitch, coke, Plant raw materials such as coal tar, fossil raw materials, phenol resin, vinyl chloride resin, vinyl acetate resin, melamine resin, urea resin, resorcinol resin, celluloid, epoxy resin, polyurethane resin, polyester resin, acrylic resin, polyamide resin, etc. Examples include various synthetic resins, synthetic rubbers such as polybutylene, polybutadiene and polychloroprene, and activated carbon obtained by carbonization and activation of activated carbon raw materials such as synthetic wood and synthetic pulp. Among these activated carbon raw materials, coconut shells are preferably used because they have high adsorption performance for the impurities (A).

The activated carbon used in the present embodiment was measured by a nitrogen adsorption method at −196 ° C. (using ASAP2405 manufactured by Micromeritics, etc.) because it has excellent adsorption performance for impurities (A). As the pore characteristics, the specific surface area is preferably 600 m ² / g to 2500 m ² / g, more preferably 1000 m ² / g to 1600 m ² / g, and the average pore diameter is 1.6 nm to The thickness is preferably 3.5 nm, more preferably 1.7 nm to 2.0 nm. The pore volume is preferably 0.25 mL / g to 1.5 mL / g, more preferably 0.3 mL / g to 1.0 mL / g.

Similarly, the activated carbon used in the present embodiment is excellent in the adsorption performance of impurities (A), and as a general physical property value measured by the JIS K1474 test method, the weight loss on drying is 5.0 mass fraction% or less. It is preferably more than 0% by mass to 5.0% by mass, and the ignition residue is preferably 5.0% by mass or less. The packing density is preferably 0.25 g / mL to 0.85 g / mL, more preferably 0.35 g / mL to 0.60 g / mL. The pH is preferably from 4.0 to 12.0, more preferably from 5.0 to 11.0. The acetone adsorption performance is preferably 14.0% by mass to 41.0% by mass, more preferably 25.0% by mass to 39.0% by mass. The iodine adsorption performance is preferably 600 mg / g to 2600 mg / g, more preferably 900 mg / g to 1600 mg / g. The hardness is preferably 90.0% by mass to 100.0% by mass.

Examples of the shape of the activated carbon used in the present embodiment include formed charcoal having a length of about 2 mm to 10 mm, crushed charcoal of about 4 mesh to 50 mesh, granular charcoal, and the like. Crushed charcoal or formed charcoal with a length of 2 mm to 5 mm is preferred. Of these, crushed activated carbon is preferable and crushed coconut shell activated carbon is particularly preferable in terms of economical advantage. As the activated carbon, a commercially available product may be used, or activated carbon produced by a known method may be used. Further, as the activated carbon, those subjected to pretreatment such as acid treatment, heat treatment, and steam treatment can be used.

(Zeolite)
The zeolite used in the present embodiment is a synthetic zeolite having a chemical composition represented by the following chemical formula [4] or [5].
K _x Na _y [(AlO ₂ ) ₁₂ (SiO ₂ ) ₁₂ ] · 27H ₂ O ............ [4]
(Here, x + y = 12, and x: y = 4: 6 to 8: 2)
K _x Na _y [(AlO ₂ ) ₈₆ (SiO ₂ ) ₁₀₆ ] · 276H ₂ O ............ [5]
(Here, x + y = 86, and x: y = 4: 6 to 8: 2)

Examples of the zeolite used in this embodiment include zeolites 3A, 4A, and 5A. Zeolite 3A, 4A and 5A are synthetic zeolites having a pore diameter of 0.25 nm to 0.45 nm.

The zeolite 3A in the present embodiment refers to a synthetic zeolite having a pore diameter of 0.28 nm ± 0.03 nm. However, due to the expansion and contraction and kinetic energy of the molecules entering the cavity at the normal operating temperature, this synthetic zeolite 3A can pass molecules having an effective diameter of 0.3 nm.

The zeolite 4A in the present embodiment refers to a synthetic zeolite having a pore diameter of 0.35 nm ± 0.03 nm.

The zeolite 5A in the present embodiment refers to a synthetic zeolite having a pore diameter of 0.42 nm ± 0.03 nm.

Examples of such zeolite include those expressed as 3A, 4A and 5A among the A-type synthetic zeolites. Commercially available products include molecular sieves 3A, 4A, 5A (trade names of Union Showa). Moreover, as a commercial item of X-type synthetic zeolite, there is molecular sieve 13X. Further, in addition to zeolite 3A, 4A or 5A, molecular sieve 13X may be used in combination. The pore diameter of the solid adsorbent can be measured by a constant volume gas adsorption method. Examples of the adsorption gas used in the constant volume gas adsorption method include N ₂ , CO ₂ , CH ₄ , H ₂ and Ar.

(silica)
In the present embodiment, silica is a compound mainly having a chemical composition of SiO ₂ . Examples of the silica include porous synthetic silica gel, mesoporous silica, silica alumina and the like. Silica may be used alone or in combination of two or more.

Examples of the shape of silica used as the solid adsorbent include powder, fine particles, granules, and thin films. The shape of the silica can be appropriately selected according to the reaction method. The shape of the silica is preferably in the form of powder or fine particles in view of the adsorption performance of the impurity (A). Among these, fine-particle silica is easy to handle because it is uniformly dispersed in a liquid purification composition to form a dispersion. Moreover, the particulate silica is easy to form an adsorption layer described later in the reactor.

The porous synthetic silica gel used in this embodiment is silica gel having pores. The shape of the porous synthetic silica gel may be crushed non-spherical or spherical, but is preferably spherical from the viewpoint of high strength and easy recycling. Further, “spherical” is not limited to a true sphere, but includes a slightly deformed sphere such as an elliptical sphere. “Spherical” is preferably an average sphericity of 0.5 or more, more preferably 0.85 or more.

The average particle diameter of the spherical porous synthetic silica gel is preferably 0.1 μm to 10,000 μm, more preferably 1 μm to 5000 μm. The average pore diameter of the spherical porous synthetic silica gel is preferably 0.5 nm to 100 nm, and more preferably 2 nm to 50 nm. The specific surface area of the spherical porous synthetic silica gel is preferably 10 m ² / g to 10000 m ² / g, more preferably 30 m ² / g to 1000 m ² / g. When the content is out of these ranges, the content of effective particles and pores may be reduced, leading to a reduction in reaction rate and a side reaction.

Porous synthetic silica gel is easily available as a commercial product, and can also be synthesized by a known method. Further, the porous synthetic silica gel may be subjected to pretreatment such as activation treatment. For example, commercially available porous synthetic silica gels include silica gel 40 and silica gel 60, which are often used as chromatographic carriers, Wakosil C-200, Wakosil C-300 manufactured by Wako Pure Chemical Industries, Ltd. Examples include silica gel.

In addition, in this specification, an average particle diameter is a value of the weight reference | standard 50% average particle diameter measured by the sieving method prescribed | regulated to JISZ8801. The specific surface area can be measured by a gas adsorption method using N ₂ , CO ₂ , CH ₄ , H ₂ , Ar, or the like.

Mesoporous silica is an inorganic substance having a uniform and regular mesopores (pores having a diameter of 2 nm to 50 nm) and mainly having a chemical composition of SiO ₂ . Examples of the shape of mesoporous silica include a spherical shape, a powder shape, a fine particle shape, and a thin film shape. Among these, spherical fine particles are more preferable from the viewpoint of a large specific surface area, high strength, easy recycling, and simple industrial production. The pore diameter of mesoporous silica is preferably 2 nm to 50 nm, and more preferably 2 nm to 10 nm. When the pore diameter of mesoporous silica is smaller than 2 nm, the diffusion rate of the purification composition into mesoporous silica is low, and the adsorption performance may be reduced. On the other hand, when the pore diameter of the mesoporous silica is larger than 50 nm, the purification composition and the mesoporous silica are not sufficiently in contact with each other, and there is a possibility that a high selectivity and a high yield cannot be obtained.

Preferably the BET specific surface area of mesoporous silica is ^{10m 2 / g ~ 3000m 2 /} g, more preferably ^{50m 2 / g ~ 3000m 2 /} g. Such mesoporous silica having a BET specific surface area can be easily produced, and can efficiently contact the purification composition and effectively adsorb the impurities (A).

The average particle size of mesoporous silica is preferably 0.2 μm to 10,000 μm, more preferably 1 μm to 5000 μm.

As typical examples of mesoporous silica, MCM-41, MCM-48, MCM-50, SBA-1, SBA-11, SBA-15, SBA-16, FSM-16, KIT-5, KIT-6, HMS (Hexagonal crystal), MSU-F, MSU-H and the like. These mesoporous silicas are commercially available and can be used. It can also be synthesized by a known method.

Silica alumina is a complex oxide mainly composed of silica (SiO ₂ ) and alumina (Al ₂ O ₃ ), and may be crystalline or amorphous. The total content of silica and alumina in the silica alumina is preferably 95% by mass or more, and the silica content is preferably 50 mol% or more.

Examples of the shape of silica alumina include a spherical shape, a powder shape, a fine particle shape, and a thin film shape. Among these, spherical fine particles are preferable from the viewpoint of a large specific surface area, high strength, easy recycling, and simple industrial production.

The average particle size of the silica alumina spherical particles is preferably 0.2 μm to 20000 μm, and more preferably 1 μm to 10,000 μm. The average pore size of the spherical alumina silica alumina is 1 nm to 100 nm, preferably 2 nm to 50 nm. The specific surface area of the silica alumina of the spherical fine particles is preferably 10 m ² / g to 10000 m ² / g, and more preferably 30 m ² / g to 1000 m ² / g. The spherical fine silica alumina having the above average particle diameter and specific surface area can be easily produced. Moreover, if it is the said average particle diameter and specific surface area, the diffusion rate of the composition for refinement | purification is high, and it is excellent in the adsorption | suction performance of an impurity (A).

Silica alumina is readily available as a commercial product and can be synthesized by a known method. Further, the silica alumina may be subjected to pretreatment such as activation treatment as necessary.

Examples of commercially available silica alumina include silica alumina 308 manufactured by Fuji Silysia Chemical Co., Ltd., N633HN, N631HN, N633L, N631L manufactured by JGC Catalysts & Chemicals, Al-MCM-41 manufactured by Sigma-Aldrich, and Al-MSU-F. It is done.

(alumina)
Alumina is a compound mainly having a chemical composition of Al ₂ O ₃ . As alumina, activated alumina is preferable. The activated alumina is an inorganic porous body and is a metastable phase alumina in the transition process from aluminum hydroxide to α-alumina, which is a high temperature stable phase. Since the specific surface area is large and the adsorption performance is excellent, the activated alumina is preferably amorphous or γ-alumina.

The shape of the activated alumina is preferably a molded body such as a spherical shape, a cylindrical shape, a prismatic shape, a tablet shape, a hollow cylindrical shape, and a honeycomb shape, and a granular material having a particle size of 3 mm to 8 mm is preferable in terms of handling. In addition, it is preferable in that the pressure loss during the solid-gas contact is minimized.

The pores contained in the activated alumina are classified into micropores (pore diameter of 20 angstroms or less), macropores (pore diameter of 500 angstroms or more), and mesopores located between the two. Of these pores, the micropores physically adsorb the impurities (A), and the mesopores and macropores are considered to alleviate the diffusion rate limiting of the purification composition. The pore volume occupied by the micropores is preferably in the range of 10% to 50% of the total pore volume. The pore diameter and volume of the mesopores and macropores in the activated alumina can be adjusted by adjusting the type of raw material and the molding conditions when producing the activated alumina.

Activated alumina, from the viewpoint of excellent adsorption performance of impurities (A), is preferably in the BET specific surface area of ^{50m 2 / g ~ 350m 2 /} g, 100m 2 / g ~ 350m 2 / g is more preferable. The average pore diameter of the activated alumina measured by the nitrogen adsorption method is preferably 5 angstroms to 200 angstroms, more preferably 10 angstroms to 150 angstroms. The pore volume of the activated alumina is preferably 0.1 mL / g to 0.8 mL / g, more preferably 0.2 mL / g to 0.5 mL / g.

(Method of contacting solid adsorbent with purification composition)
In the manufacturing method of this embodiment, the impurity (A) in the composition for purification is adsorbed to the solid adsorbent by bringing the composition for purification containing 1233yd and the impurity (A) into contact with the solid adsorbent described above. Removed.

The composition for purification at the time of contacting with the solid adsorbent may be gas (gaseous) or liquid (liquid). In the production method of the present embodiment, when two or more solid adsorbents are used in combination, the order of the solid adsorbents to be contacted is not particularly limited. For example, the purification composition may be brought into contact with two or more kinds of solid adsorbents in order, or may be brought into contact at the same time by mixing two or more kinds of solid adsorbents. When contacting in order, about each of the solid adsorbents used, the composition for purification and the solid adsorbent may be brought into contact with each other by a contact method described later.

Hereinafter, a method using a gaseous purification composition will be described as an example. In this method, for example, a solid adsorbent is filled in a reactor to form an adsorption layer, and a gaseous purification composition containing 1233yd is circulated through the adsorption layer to thereby produce a solid adsorbent and a purification layer. The composition can be contacted. The contact between the solid adsorbent and the purification composition by this method may be batch (batch) or continuous.

The packing density of the solid adsorbent in the adsorption layer is preferably 0.1 g / cm ³ or more, and more preferably 0.25 g / cm ³ or more. If the packing density of the solid adsorbent is equal to or higher than the lower limit value, the amount of the solid adsorbent per unit volume is increased, and the amount of treatment of the gaseous purification composition can be increased. Removal efficiency is improved. There may be one adsorption layer or two or more adsorption layers. When there are two or more adsorbing layers, the adsorbing layers may be in parallel or in series.

The temperature of the adsorption layer at the time of contact is preferably 60 ° C. to 100 ° C., more preferably 70 ° C. to 90 ° C., which is not less than the boiling point of 1233yd, in order to maintain the purification composition in a gas state. If the temperature of the adsorption layer is at least the lower limit value, the removal efficiency of the impurities (A) by the solid adsorbent is improved. If the temperature of the adsorption layer is not more than the upper limit value, less energy is required for cooling the composition after purification, and facilities and the like are simplified.

The pressure in the reactor at the time of contact (gauge pressure, the same applies hereinafter) is preferably 10 kPa to 500 kPa, more preferably 90 kPa to 300 kPa. If a pressure is more than a lower limit, the removal efficiency of an impurity (A) will improve. If the pressure is below the upper limit, the handling is good and the equipment is simple.

The contact time between the gaseous purification composition to be passed through the adsorption layer and the adsorption layer is preferably 1 second to 1000 seconds, and more preferably 3 seconds to 300 seconds. If the contact time between the gaseous purification composition and the adsorption layer is equal to or greater than the lower limit, the removal efficiency of impurities (A) is improved. If the contact time between the gaseous purification composition and the adsorption layer is less than or equal to the upper limit, the adsorption layer used for the purification of the purification composition can be small, so that the facilities and the like are simplified. In the method of circulating the purification composition containing 1233yd in the adsorption layer, the contact time corresponds to the residence time of the purification composition in the reactor, and the supply amount of the purification composition to the reactor It can be controlled by adjusting (flow rate). The same applies to the case of using a liquid purification composition described later.

From the viewpoint of removal efficiency, the total amount of impurities (A) contained in the gaseous purification composition to be circulated through the adsorption layer is 0.05 mass relative to 1 mass part of the solid adsorbent in the adsorption layer. Part or less, preferably 0.02 part by weight or less. That is, in the method using the gaseous purification composition, the amount of the gaseous purification composition brought into contact with the solid adsorbent is such that the ratio of the impurities (A) to the solid adsorbent is not more than the above upper limit. It is preferable to adjust the contact.

The reactor used for contacting the purification composition gas with the solid adsorbent may be any reactor that can be filled with the solid adsorbent to form an adsorption layer. Examples of the material of the reactor include glass, iron, nickel, an alloy containing these as a main component, and a fluororesin such as tetrafluoroethylene-perfluoro (alkyl vinyl ether) copolymer (PFA).

Next, a method of using a liquid purification composition will be described. In this method, similarly to the method using the gaseous purification composition, it is possible to use a method in which an adsorption layer is formed in the reactor and a liquid purification composition containing 1233yd is circulated in the adsorption layer. it can. Moreover, the method of immersing a solid adsorbent in the composition for refinement | purification in the reactor containing the solid adsorbent, and mixing and stirring as needed can be used. The contact between the solid adsorbent and the purification composition by these methods may be batch (batch) or continuous.

When the purification composition is brought into contact with the solid adsorbent in a liquid state, the purification composition can be made liquid by adjusting it to a temperature below the boiling point at normal pressure. Moreover, the composition for purification can be dissolved in a solvent to make it liquid. As a solvent used at this time, a solvent having a boiling point different from that of 1233yd can be easily removed from the purified composition by a method such as distillation.

The temperature in the reactor at the time of contact between the solid adsorbent and the purification composition is preferably −30 ° C. to 70 ° C., more preferably 10 ° C. to 40 ° C. If the temperature in the reactor is equal to or higher than the lower limit, the removal rate of impurities other than 1233yd is improved. If the temperature in the reactor is equal to or lower than the upper limit value, less energy is required for cooling the purified composition, and facilities and the like are simplified.

The pressure in the reactor at the time of contact between the solid adsorbent and the purification composition is preferably 0 kPa to 200 kPa, more preferably 100 kPa to 150 kPa. If the pressure is equal to or higher than the lower limit value, the removal rate of impurities other than 1233yd is improved. If the pressure is below the upper limit, the handling is good and the equipment is simple.

In the method of circulating the purification composition containing 1233yd in the adsorption layer, the contact time between the liquid purification composition to be circulated in the adsorption layer and the adsorption layer is preferably 1 second to 1000 seconds, and 3 seconds to 300 seconds. Is more preferable. If the contact time between the liquid purification composition and the adsorption layer is equal to or greater than the lower limit, the removal efficiency of the impurities (A) is improved. If the contact time between the liquid purification composition and the adsorption layer is less than or equal to the upper limit, the adsorption layer used for the purification of the composition can be small, and thus the facilities and the like are simplified.

The preferred embodiment of the packing density of the solid adsorbent in the adsorption layer and the constitution of the adsorption layer is the same as the method using the gaseous purification composition.

In the method of immersing the solid adsorbent in the purification composition in the reactor containing the solid adsorbent, the contact time between the liquid purification composition and the solid adsorbent in the reactor is 1 hour to 100 hours. 3 hours to 60 hours is more preferable. If the contact time between the liquid purification composition and the solid adsorbent is at least the lower limit, the removal efficiency of impurities (A) is improved. If the contact time between the liquid purification composition and the solid adsorbent is less than or equal to the upper limit, the amount of the solid adsorbent used for purification of the purification composition can be reduced, so that the facilities and the like are simplified.

In the method of immersing the solid adsorbent in the purification composition in the reactor, the purified composition and the solid adsorbent can be separated by precipitation or filtration after the purification composition is purified.

Moreover, from the point which the removal efficiency of an impurity (A) improves, the total amount of the impurity (A) contained in the liquid refinement | purification composition contacted with a solid adsorbent is 0 with respect to 1 mass part of a solid adsorbent. 0.05 parts by mass or less is preferable, and 0.02 parts by mass or less is more preferable. That is, in the method using the liquid purification composition, the amount of the purification composition that is brought into contact with the solid adsorbent is adjusted so that the ratio of the impurity (A) to the solid adsorbent is not more than the upper limit. It is preferable to make it contact.

As the reactor used for contacting the liquid purification composition and the solid adsorbent, for example, any reactor capable of containing the solid adsorbent or capable of forming an adsorption layer made of the solid adsorbent may be used. Examples of the material of the reactor include glass, iron, nickel, an alloy containing these as a main component, and a fluororesin such as tetrafluoroethylene-perfluoro (alkyl vinyl ether) copolymer (PFA). Examples of the reactor for mixing and contacting the mixed liquid with the solid adsorbent include a reactor capable of bringing the purification composition into contact with the solid adsorbent in a liquid state at a desired temperature and pressure, such as an autoclave. .

(Composition after purification)
In general, solid adsorbents are easily adsorbed depending on the composition of the composition to be purified and the type of solid adsorbent (substance composition and pore size). In the present embodiment where a composition comprising 1233yd and one or more compounds selected from water, 1-chloro-3,3-difluoro-1-propyne, oxide and HCFC-244ca is to be purified, for example, water Is easily adsorbed on zeolite, preferably zeolite 3A or zeolite 4A. Water is also easily adsorbed by alumina and silica. Therefore, in the purification of this embodiment, alumina, silica, or zeolite (particularly, zeolite 3A or 4A) is used as the solid adsorbent, and the water in the composition is brought into contact with the composition for purification containing 1233yd and water. Can be selectively removed to purify 1233yd.

Oxides in the purification composition are easily adsorbed on activated carbon and alumina. Therefore, in the manufacturing method of this embodiment, activated carbon or alumina is used as a solid adsorbent, and 1233yd can be produced by selectively removing oxide by contacting with a purification composition containing 1233yd and oxide. it can.

Also, 1-chloro-3,3-difluoro-1-propyne in the composition for purification is easily adsorbed on activated carbon, silica, and alumina. Therefore, by using activated carbon, silica or alumina as a solid adsorbent and bringing it into contact with a purification composition containing 1233yd and 1-chloro-3,3-difluoro-1-propyne, Chloro-3,3-difluoro-1-propyne can be efficiently removed to produce 1233yd.

In addition, HCFC-244ca in the purification composition is easily adsorbed on activated carbon, alumina, and zeolites 4A and 5A. Therefore, activated carbon, zeolite 4A, or zeolite 5A is used as the solid adsorbent, and the HCFC-244ca is efficiently removed from the purification composition by contacting with the purification composition containing 1233yd and HCFC-244ca. 1233yd can be manufactured.

In this way, by using one kind of solid adsorbent alone or in combination of two or more kinds, it is possible to remove a desired compound from the impurities (A) contained in the purification composition to a desired extent. it can.

By removing the impurity (A) contained in the purification composition by the production method of the present embodiment, a composition in which the content of the impurity (A) is reduced can be obtained.
Moreover, it is preferable that content of 1233yd in the composition after refine | purifying with the manufacturing method of this embodiment is 90 mass% or more, 95 mass% or more is more preferable, 99 mass% or more is further more preferable. The content of water in the purified composition is preferably 0.005% by mass or less, and the content of 1-chloro-3,3-difluoro-1-propyne is 0.001% by mass or less. It is preferably 0.0005% by mass or less, and more preferably 0.0003% by mass or less. Further, the content of HCFC-244ca in the composition after purification is preferably 0.1% by mass or less, and more preferably 0.058% by mass or less. If each component is less than or equal to the upper limit, various performances in each application can be exhibited. The oxide content in the composition after purification is preferably 5 ppm by mass or less. If content of an oxide is below the said upper limit, the fall of stability of a solvent composition can fully be prevented. Moreover, if content of an oxide is below the said upper limit, it does not need to reduce to the limit of 0 mass ppm. 1 mass ppm or more is preferable and, as for content of the oxide in the composition after refinement | purification, 2 mass ppm or more is more preferable. If it is more than the said lower limit, oxidation of 1233yd is suppressed and it is excellent in stability of a solvent composition.

<Second Embodiment>
The manufacturing method of 1233yd which is the 2nd Embodiment of this invention has the process of manufacturing the composition for refinement | purification containing 1233yd.

In the production method of the present embodiment, a reaction product obtained in the production step 1233yd shown in (I) or (II), or a mixed composition obtained by removing acidic substances from the reaction product is used as a purification composition. be able to. By performing the purification shown in the first embodiment on the purification composition, the impurity (A) can be efficiently removed from the composition containing 1233yd and the impurity (A). .

(I) Method of reacting HCFC-244ca with hydrogen fluoride in a gas phase in a nitrogen stream using chromium oxide as a catalyst Catalyst layer filled with a chromium oxide catalyst with a raw material composition containing HCFC-244ca and hydrogen fluoride Is reacted in the gas phase to produce a composition containing 1233yd.

In such a gas phase catalytic reaction of HCFC-244ca and hydrogen fluoride, a reaction product containing 1233yd and an acidic substance such as hydrogen chloride can be obtained. And the acidic substance contained in the reaction product can be removed by alkali washing or the like to obtain a mixed composition. Compounds other than 1233yd contained in the mixed composition include HCFC-244ca, which is an unreacted raw material, water, 1-chloro-3,3-difluoro-1-propyne, HCFC-245ca, 2, 3, 3 Examples thereof include compounds such as trifluoropropene (H ₂ C═CF—CHF ₂ ), 1,2,3,3-tetrafluoropropene (HFC═CF—CHF ₂ ), and oxide.

By using the reaction product or the mixed composition thus obtained as a purification composition and performing the purification shown as the first embodiment, the impurities (A) in the purification composition can be efficiently removed. Can be removed. Other components other than 1233yd contained in the reaction product or mixed composition and contained in the purified composition can be removed to a desired extent by known means such as distillation. Further, HCFC-244ca separated from the 1233yd by the solid adsorbent can be recycled as a part of the raw material by being diffused from the solid adsorbent and recovered.

(II) A method of dehydrofluorinating HCFC-244ca at a temperature of 40 ° C. to 80 ° C. using potassium hydroxide or sodium hydroxide as a reactant. HCFC-244ca in an aqueous potassium hydroxide solution or an aqueous sodium hydroxide solution By performing a dehydrofluorination reaction at a temperature of 40 ° C. to 80 ° C., a composition containing 1233yd is produced. In the above reaction, it is preferable to carry out a dehydrofluorination reaction in the presence of a phase transfer catalyst for the purpose of promoting the reaction. The amount of potassium hydroxide or sodium hydroxide in the potassium hydroxide aqueous solution or sodium hydroxide aqueous solution is preferably 1 to 3 times the molar amount of HCFC-244ca.

In such a synthesis method in which HCFC-244ca is subjected to dehydrofluorination reaction at a temperature of 40 ° C. to 80 ° C. using potassium hydroxide or sodium hydroxide as a reaction agent, a reaction product containing 1233yd can be obtained. Examples of compounds other than 1233yd contained in the reaction product include compounds such as water, 1-chloro-3,3-difluoro-1-propyne, and oxide in addition to HCFC-244ca which is an unreacted raw material.

The impurities (A) in the purification composition can be efficiently removed by using the reaction product thus obtained as the purification composition and carrying out the purification shown as the first embodiment. Other components other than 1233yd contained in the reaction product and in the purified composition can be removed to a desired extent by known means such as distillation. Further, HCFC-244ca separated from the 1233yd by the solid adsorbent can be recycled as a part of the raw material by being diffused from the solid adsorbent and recovered.

Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to these examples.

(Analysis method)
The content (content ratio) of components other than water and hydroperoxide in the composition to be analyzed is analyzed by gas chromatography. DB-1301 (length 60 m × inner diameter 250 μm × thickness 1 μm, manufactured by Agilent Technologies) is used as the column. The water content is analyzed with a Karl Fischer moisture meter, and the hydroperoxide content is analyzed by the hydroperoxide measurement method described above.

Further, by using the analysis results of the gas chromatography, Karl Fischer moisture meter and hydroperoxide measurement method, the ratio of 1-chloro-3,3-difluoro-1-propyne to the total amount of the composition to be analyzed (mass%) ), Water (mass%), oxide (mass ppm), and HCFC-244ca (mass%).
The oxide content is the total amount of the analysis results obtained by the gas chromatography and hydroperoxide measurement methods.

(Production example: production of 1233yd)
Using 2000 g of HCFC-244ca as a raw material, 19.9 g of tetra-n-butylammonium chloride was added, and the reaction temperature was kept at 50 ° C., and 2792 g of 40 mass% potassium hydroxide aqueous solution was added dropwise over 30 minutes. Thereafter, the reaction was continued for 52 hours, the organic phase and the aqueous phase were separated into two phases, and the organic phase was recovered. The recovered organic phase was roughly distilled and the fraction was recovered to obtain a composition (purification composition) containing 1233yd, water, 1-chloro-3,3-difluoro-1-propyne and oxide.

Example 1
The content of oxide in the purification composition containing 1233yd obtained in the above production example was quantified by the above gas chromatography and hydroperoxide measurement method. As a result, 3-chloro-2- (difluoromethyl) -2- It was found that 39 mass ppm of oxide was contained in total of 20 mass ppm of fluorooxirane and 19 mass ppm of hydroperoxide. For this reason, 1% by mass of activated carbon (manufactured by Cerachem Co., Ltd., coconut shell-based crushed activated carbon, product name: Fuji Carbon B-) is added to the above-mentioned oxide-containing purification composition in 1 kg of 1233yd in the purification composition. CW) was added and allowed to stand at room temperature for 48 hours. After 48 hours, the activated carbon was separated from 1233yd and the content of oxide was measured. As a result, 3-chloro-2- (difluoromethyl) -2-fluorooxirane was 0 ppm by mass, hydroperoxide was 2.2 ppm by mass, The total was 2.2 mass ppm.

(Example 2)
In the above-mentioned purification composition containing 39 mass ppm of oxide, 1% by mass of activated alumina per 1 kg of 1233yd in the purification composition (manufactured by Fuji Co., Ltd., activated alumina, product name PSG-D25) And left at room temperature for 48 hours. After 48 hours, activated alumina was separated from 1233yd and the content of oxide was measured. As a result, 3-chloro-2- (difluoromethyl) -2-fluorooxirane was 0 ppm by mass, and hydroperoxide was 3.2 ppm by mass. The total was 3.2 ppm by mass.

From Examples 1 and 2, it was revealed that the oxide can be effectively removed from the purification composition by bringing activated carbon or activated alumina into contact with the purification composition containing 1233yd.

(Example 3)
The composition other than oxide in the composition for purification containing 1233yd obtained by the above production example was analyzed, and the composition shown in Table 1 showed 1233yd, water, 1-chloro-3,3-difluoro-1-propyne and HCFC. -244ca is included. 1233yd of the composition ratio shown in Table 1 is put into a polypropylene container with a 1 L lid, and 1% by mass of activated carbon (made by Serachem Corp., coconut shell system) is added to 1kg of 1233yd in the composition for purification. Crushed activated carbon, product name: Fuji Carbon B-CW) is added and allowed to stand at room temperature for 48 hours. After 48 hours, when activated carbon is separated from the purification composition and the composition other than oxide is analyzed, the composition shown in Table 1 is obtained.

Example 4
The treatment is performed in the same manner as in Example 3 except that activated alumina (manufactured by Fuji Co., Ltd., activated alumina, product name PSG-D25) is used instead of activated carbon. After the treatment, when activated alumina is separated from the purification composition and the composition other than oxide is analyzed, the composition shown in Table 1 is obtained.

(Example 5)
The treatment is performed in the same manner as in Example 3 except that zeolite 3A (trade name: Molecular Sieve 3A, manufactured by Union Showa) is used instead of activated carbon. After the treatment, when zeolite 3A is separated from the purification composition and the composition other than oxide is analyzed, the composition shown in Table 1 is obtained.

(Example 6)
The treatment is performed in the same manner as in Example 3 except that zeolite 4A (trade name: Molecular Sieve 4A, manufactured by Union Showa) is used instead of activated carbon. After the treatment, when the zeolite 4A is separated from the purification composition and the composition other than oxide is analyzed, the composition shown in Table 2 is obtained.

(Example 7)
The treatment is performed in the same manner as in Example 3 except that zeolite 5A (trade name: Molecular Sieve 5A, manufactured by Union Showa) is used instead of activated carbon. After the treatment, when zeolite 5A is separated from the composition for purification and the composition other than oxide is analyzed, the composition shown in Table 2 is obtained.

(Example 8)
The treatment is performed in the same manner as in Example 3 except that silica gel (Kanto Chemical Co., Inc., trade name: spherical silica gel (particle size 63-210 μm)) is used instead of activated carbon. After the treatment, when silica gel is separated from the purification composition and the composition other than oxide is analyzed, the composition shown in Table 2 is obtained.

From Examples 3 to 8, the purification composition containing 1233yd is brought into contact with activated carbon, alumina, zeolite 3A, zeolite 4A, zeolite 5A, and silica gel, whereby water, 1-chloro-3,3 It can be seen that -difluoro-1-propyne and HCFC-244ca can be effectively removed. In particular, it is highly effective to use alumina, zeolite 3A, zeolite 4A, zeolite 5A or silica gel to remove water from the purification composition, and 1-chloro-3,3-difluoro-1 from the purification composition is highly effective. -It can be seen that the use of activated carbon, alumina, zeolite 5A or silica gel is effective in removing propyne. Furthermore, it can be seen that the use of activated carbon, alumina, zeolite 4A, and zeolite 5A is effective in removing HCFC-244ca.

According to the method for producing 1-chloro-2,3,3-trifluoropropene of the present invention, 1-chloro-2,3,3-trifluoropropene, water, 1-chloro-3,3-difluoro- Efficient removal of water, 1-chloro-3,3-difluoro-1-propyne, oxide and HCFC-244ca from a composition comprising 1-propyne, oxide and one or more compounds selected from HCFC-244ca can do.
Further, according to the production method of the present invention, 1-chloro-2,3,3-trifluoropropene, water, From a composition comprising 1-chloro-3,3-difluoro-1-propyne, oxide and one or more compounds selected from HCFC-244ca, water, 1-chloro-3,3-difluoro-1-propyne, Since oxide and HCFC-244ca can be efficiently removed, 1-chloro-2,3,3-trifluoropropene can be produced efficiently.

Claims (8)

1. Selected from 1-chloro-2,3,3-trifluoropropene and water, 1-chloro-3,3-difluoro-1-propyne, oxide and 3-chloro-1,1,2,2-tetrafluoropropane 1-chloro-2,3,3-trifluoropropene, wherein the composition comprising at least one compound is contacted with a solid adsorbent to remove the compound contained in the composition Manufacturing method.
2. The method for producing 1-chloro-2,3,3-trifluoropropene according to claim 1, wherein the solid adsorbent contains at least one selected from activated carbon, zeolite, silica and alumina.
3. The 1-chloro-2 according to claim 1 or 2, wherein the composition contains water, the solid adsorbent contains at least one selected from zeolite, silica and alumina, and removes the water from the composition. , 3,3-trifluoropropene production method.
4. The 1- of any one of claims 1 to 3, wherein the composition contains an oxide, the solid adsorbent contains at least one selected from activated carbon and alumina, and removes the oxide from the composition. A method for producing chloro-2,3,3-trifluoropropene.
5. The oxide is 3-chloro-2- (difluoromethyl) -2-fluorooxirane, 2,2-difluoroacetyl fluoride, formyl chloride, 1-chloro-2,3,3-trifluoro-1-hydroperoxy E-form of -1-propene, Z-form of 1-chloro-2,3,3-trifluoro-1-hydroperoxy-1-propene, 3-chloro-1,1,2-trifluoro-3-hydro Peroxy-1-propene, E-form of 1-chloro-2,3,3-trifluoro-3-hydroperoxy-1-propene, 1-chloro-2,3,3-trifluoro-3-hydroper The process for producing 1-chloro-2,3,3-trifluoropropene according to any one of claims 1 to 4, which is at least one selected from Z-forms of oxy-1-propene.
6. The composition contains 1-chloro-3,3-difluoro-1-propyne, the solid adsorbent contains at least one selected from activated carbon, silica and alumina, and the composition contains 1-chloro-3, The method for producing 1-chloro-2,3,3-trifluoropropene according to any one of claims 1 to 5, wherein 3-difluoro-1-propyne is removed.
7. The composition includes 3-chloro-1,1,2,2-tetrafluoropropane, and the solid adsorbent includes at least one selected from activated carbon, alumina, zeolite 4A, and zeolite 5A. The process for producing 1-chloro-2,3,3-trifluoropropene according to any one of claims 1 to 6, wherein 3-chloro-1,1,2,2-tetrafluoropropane is removed.
8. 3-chloro-1,1,2,2-tetrafluoropropane is dehydrofluorinated to give 1-chloro-2,3,3-trifluoropropene and water, 1-chloro-3,3-difluoro The method further comprises the step of producing a composition comprising: at least one compound selected from 1-propyne, oxide and 3-chloro-1,1,2,2-tetrafluoropropane. A process for producing -chloro-2,3,3-trifluoropropene according to claim 1.