CN109937196B - Method for producing 1-chloro-2, 3, 3-trifluoropropene - Google Patents
Method for producing 1-chloro-2, 3, 3-trifluoropropene Download PDFInfo
- Publication number
- CN109937196B CN109937196B CN201780070437.4A CN201780070437A CN109937196B CN 109937196 B CN109937196 B CN 109937196B CN 201780070437 A CN201780070437 A CN 201780070437A CN 109937196 B CN109937196 B CN 109937196B
- Authority
- CN
- China
- Prior art keywords
- chloro
- composition
- oxide
- purification
- solid adsorbent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/25—Preparation of halogenated hydrocarbons by splitting-off hydrogen halides from halogenated hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/38—Separation; Purification; Stabilisation; Use of additives
- C07C17/389—Separation; Purification; Stabilisation; Use of additives by adsorption on solids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C21/00—Acyclic unsaturated compounds containing halogen atoms
- C07C21/02—Acyclic unsaturated compounds containing halogen atoms containing carbon-to-carbon double bonds
- C07C21/18—Acyclic unsaturated compounds containing halogen atoms containing carbon-to-carbon double bonds containing fluorine
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The present invention provides a method for producing 1-chloro-2, 3, 3-trifluoropropene, which efficiently removes 1 or more compounds selected from the group consisting of water, 1-chloro-3, 3-difluoro-1-propyne, an oxide and HCFC-244ca from a composition containing 1-chloro-2, 3, 3-trifluoropropene, thereby efficiently producing 1-chloro-2, 3, 3-trifluoropropene. A process for producing 1-chloro-2, 3, 3-trifluoropropene, which comprises contacting a composition comprising 1-chloro-2, 3, 3-trifluoropropene and at least 1 compound selected from the group consisting of water, 1-chloro-3, 3-difluoro-1-propyne, an oxide and 3-chloro-1, 1,2, 2-tetrafluoropropane with a solid adsorbent to remove the compound contained in the composition.
Description
Technical Field
The present invention provides a process for producing 1-chloro-2, 3, 3-trifluoropropene, which comprises removing impurities other than 1-chloro-2, 3, 3-trifluoropropene from a composition comprising 1-chloro-2, 3, 3-trifluoropropene and 1 or more compounds selected from the group consisting of water, 1-chloro-3, 3-difluoro-1-propyne, an oxide and 3-chloro-1, 1,2, 2-tetrafluoropropane.
Background
Hydrochlorofluorocarbons (HCFCs) have a negative impact on the ozone layer and therefore their production is planned to be limited. HCFCs include, for example, 3-dichloro-1, 1,1,2, 2-pentafluoropropane (HCFC-225ca) and 1, 3-dichloro-1, 1,2,2, 3-pentafluoropropane (HCFC-225cb), and with the restriction on HCFCs, it is desired to develop compounds that substitute for the above-mentioned HCFCs.
An example of the compound substituting for HCFC is 1-chloro-2, 3, 3-trifluoropropene (HClC ═ CF-CHF) 2 HCFO-1233 yd). 1233yd has a low greenhouse potential (GWP), and is a compound useful for cleaning agents, solvents, refrigerants, blowing agents, and aerosol applications.
In contrast, patent document 1 discloses a process for producing 1,1,2,2, 3-pentafluoropropane (HCFC-245ca) by reacting 3-chloro-1, 1,2, 2-tetrafluoropropane (HCFC-244ca) with hydrogen fluoride in a gas phase under a nitrogen gas stream using chromium hydroxide as a catalyst. 1233yd was produced as a by-product in this process. Therefore, by recovering the composition obtained by the above reaction to separate 1233yd contained in the composition, a composition containing 1233yd can be obtained. The composition containing 1233yd so obtained can be used in cleaning agents, solvents, refrigerants, blowing agents or aerosol applications.
However, the composition containing 1233yd obtained by the above production method may contain HCFC-244ca as an unreacted raw material, 1-chloro-3, 3-difluoro-1-propyne produced as a by-product in the production process, water, an oxide produced by oxidizing 1233yd with oxygen in the air, or the like.
When the composition containing 1233yd is used as a cleaning agent, a solvent, a refrigerant, a blowing agent, or an aerosol, various problems in terms of reliability and performance may be caused if the composition containing 1233yd contains water, 1-chloro-3, 3-difluoro-1-propyne, HCFC-244ca, or the like at a high concentration. In order to reduce such adverse effects, it is preferable to reduce the amounts of water, 1-chloro-3, 3-difluoro-1-propyne, HCFC-244ca, and the like contained in the composition containing 1233yd as much as possible.
In addition, when the 1233 yd-containing composition is used as a cleaning agent, a solvent, a refrigerant, a foaming agent, or an aerosol, if the 1233 yd-containing composition contains an oxide at a high concentration, problems such as a decrease in stability and generation of an acidic substance may occur. To suppress such adverse effects, it is preferable to reduce the amount of oxide mixed in the composition containing 1233yd as much as possible.
However, comparative document 1 does not describe a method for efficiently removing water, 1-chloro-3, 3-difluoro-1-propyne and an oxide from a composition containing 1233 yd.
Documents of the prior art
Patent document
Patent document 1: international publication No. 1994/014737
Disclosure of Invention
Technical problem to be solved by the invention
The present invention has been made in view of the above-mentioned circumstances, and an object of the present invention is to provide a method for producing 1233yd, which is capable of efficiently removing 1 or more compounds selected from the group consisting of water, 1-chloro-3, 3-difluoro-1-propyne, an oxide and HCFC-244ca from a composition containing 1233yd and 1 or more compounds selected from the group consisting of water, 1-chloro-3, 3-difluoro-1-propyne, an oxide and HCFC-244 ca.
Technical scheme for solving technical problem
The process for producing 1-chloro-2, 3, 3-trifluoropropene (HCFO-1233yd, hereinafter also abbreviated as "1233 yd") according to the present invention is characterized by contacting a composition containing 1-chloro-2, 3, 3-trifluoropropene and at least 1 compound selected from the group consisting of water, 1-chloro-3, 3-difluoro-1-propyne, an oxide and 3-chloro-1, 1,2, 2-tetrafluoropropane with a solid adsorbent to remove the compound contained in the composition.
In the process for producing 1-chloro-2, 3, 3-trifluoropropene of the present invention, it is preferable that the solid adsorbent contains at least 1 selected from the group consisting of activated carbon, zeolite, silica and alumina.
In the method for producing 1-chloro-2, 3, 3-trifluoropropene of the present invention, it is preferable that the composition contains water, and the solid adsorbent contains at least 1 selected from the group consisting of zeolite, silica, and alumina, to remove the water from the composition.
In the process for producing 1-chloro-2, 3, 3-trifluoropropene of the present invention, it is preferable that the composition contains an oxide, and the solid adsorbent contains at least 1 selected from the group consisting of activated carbon and alumina, to remove the oxide from the composition.
In the process for producing 1-chloro-2, 3, 3-trifluoropropene of the present invention, it is preferable that the oxide is selected from the group consisting of E-form of 3-chloro-2- (difluoromethyl) -2-fluoroethylene oxide, 2-difluoroacetylfluoride, formyl chloride, 1-chloro-2, 3, 3-trifluoro-1-peroxy (hydroxy) -1-propene, Z-form of 1-chloro-2, 3, 3-trifluoro-1-peroxy-1-propene, 3-chloro-1, 1, 2-trifluoro-3-peroxy-1-propene, E-form of 1-chloro-2, 3, 3-trifluoro-3-peroxy-1-propene, and E-form of 1-chloro-2, 3, 3-trifluoro-1-propene, At least one compound represented by formula Z of 1-chloro-2, 3, 3-trifluoro-3-peroxy-1-propene.
In the method for producing 1-chloro-2, 3, 3-trifluoropropene of the present invention, it is preferable that the composition contains 1-chloro-3, 3-difluoro-1-propyne, and the solid adsorbent contains at least 1 selected from the group consisting of activated carbon, silica and alumina, so as to remove the 1-chloro-3, 3-difluoro-1-propyne from the composition.
In the process for producing 1-chloro-2, 3, 3-trifluoropropene of the present invention, it is preferable that the composition contains 3-chloro-1, 1,2, 2-tetrafluoropropane, and the solid adsorbent contains at least 1 selected from the group consisting of activated carbon, alumina, zeolite 4A, and zeolite 5A, so as to 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 further comprises a step of dehydrofluorinating 3-chloro-1, 1,2, 2-tetrafluoropropane to produce a composition containing 1-chloro-2, 3, 3-trifluoropropene and at least 1 compound selected from the group consisting of water, 1-chloro-3, 3-difluoro-1-propyne, an oxide, and 3-chloro-1, 1,2, 2-tetrafluoropropane.
Effects of the invention
The production method of the present invention enables to efficiently remove 1 or more compounds selected from water, 1-chloro-3, 3-difluoro-1-propyne, oxides and HCFC-244ca from a composition containing 1233yd and 1 or more compounds selected from water, 1-chloro-3, 3-difluoro-1-propyne, oxides and HCFC-244 ca.
In addition, the production method of the present invention can efficiently produce 1233yd having high purity.
Detailed Description
Embodiments of the present invention will be described below.
< embodiment 1 >
The method for producing 1233yd according to embodiment 1 of the present invention is a method for producing 1233yd, which comprises contacting a composition containing 1233yd and 1 or more compounds selected from the group consisting of water, 1-chloro-3, 3-difluoro-1-propyne, an oxide and HCFC-244ca with a solid adsorbent to remove the 1 or more compounds selected from the group consisting of water, 1-chloro-3, 3-difluoro-1-propyne, an oxide and HCFC-244 ca. Hereinafter, the "1 or more compounds selected from water, 1-chloro-3, 3-difluoro-1-propyne, an oxide and HCFC-244 ca" are also referred to as "impurities (a)", and a composition containing 1233yd and the impurities (a) is also referred to as a "composition for purification". By bringing the purification composition into contact with a solid adsorbent, the impurity (a) is removed from the purification composition, and 1233yd is purified, whereby 1233yd having high purity can be produced. Here, as for the removal of the impurity (a), a part thereof may be removed, or the whole may be removed.
[ composition for purification ]
The purification composition of the present embodiment may contain 1233yd and the impurity (a), and is not particularly limited. The purification composition may contain other components than 1233yd and the impurity (a). The other components are by-products generated in the production process of 1233yd, and the like. The purification composition may be liquid or gaseous.
As the purification composition of 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 described later, in the case where the reaction product contains 1233yd and the impurity (a) in the production process of 1233yd, the reaction product can be used as it is as a purification composition. In addition, the reaction product can be subjected to water washing or alkali washing, and the reaction product after removing the 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, as the purification composition to be brought into contact with the solid adsorbent, a reaction product containing 1233yd obtained by the following method (I) or (II) may be specifically mentioned.
(I) Method for making HCFC-244ca react with hydrogen fluoride in gas phase under nitrogen flow by using chromic oxide as catalyst
(II) dehydrofluorination of HCFC-244ca at 40-80 deg.C with potassium hydroxide or sodium hydroxide as reactant
(1233yd)
1233yd is a fluoroolefin having a double bond between carbon atom and carbon atom, and thus has a short life in the atmosphere, low ozone depletion potential and low greenhouse potential.
1233yd exists as geometric isomers of Z-form and E-form depending on the position of the substituent on the double bond. In the present specification, unless otherwise specified, the compound name or abbreviation of the compound indicates any of the Z formula, the E formula, and the mixture of the Z formula and the E formula, and when the compound name or abbreviation of the compound is denoted by (E) or (Z), the E formula or the Z formula of each compound is indicated. For example, 1233yd (Z) represents a form Z, and 1233yd (E) represents a form E.
1233yd (Z) has a boiling point of about 54 ℃ and 1233yd (E) has a boiling point of about 48 ℃, and both compounds have excellent drying properties. Even if the steam is boiled to form steam, the steam temperature is near the boiling point of each of the components, and therefore, the components are less likely to be adversely affected by heat. In addition, 1233yd has excellent performance as a cleaning solvent and a coating solvent, such as no ignition point, low surface tension and viscosity, and easy evaporation even at normal temperature.
The purification composition of the present embodiment may contain a trace amount of 1233yd, but the content of 1233yd is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 50% by mass or more, particularly preferably 70% by mass or more, and most preferably 80% by mass or more, based on the total amount of the purification composition. If the content of 1233yd is not less than the lower limit, the removal efficiency of the impurity (A) is good. The content of 1233yd and the impurity (a) in the purification composition of the present embodiment is not particularly limited, but the molar ratio (impurity (a))/(1233yd) is preferably less than 1, more preferably 0.001 to 0.7, and even more preferably 0.1 to 0.2, from the viewpoint of the removal efficiency of the impurity (a).
(Water)
The purification composition of the present embodiment may contain, for example, water produced in the production process of 1233yd or water mixed in when the reaction product obtained in the production process of 1233yd is washed with water or alkali. When the purification composition contains water, the content of water in the purification composition 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, relative to the total amount of the purification composition, from the viewpoint of the removal efficiency of the impurity (a).
(1-chloro-3, 3-difluoro-1-propyne)
The purification composition may contain 1-chloro-3, 3-difluoro-1-propyne which is produced as a by-product in the production process of 1233 yd. 1-chloro-3, 3-difluoro-1-propyne is produced by performing a dehydrofluorination reaction of 1233yd represented by the following formula [1 ].
CHCl＝CFCHF 2 →CCl≡CCHF 2 +HF…[1]
When the purification composition contains 1-chloro-3, 3-difluoro-1-propyne, the content of 1-chloro-3, 3-difluoro-1-propyne in the purification composition 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, relative to the total amount of the purification composition, from the viewpoint of the removal efficiency of the impurity (a).
(oxide)
The purification composition of the present embodiment may contain an oxide.
The oxide (oxide) is an oxide formed by reacting 1233yd with oxygen. Specifically, the compound may include 3-chloro-2- (difluoromethyl) -2-fluoroethylene oxide (formula (a)), 2-difluoroacetylfluoride (formula (B)), formyl chloride (formula (C)), (E, Z) -1-chloro-2, 3, 3-trifluoro-1-peroxy-1-propene (formula (D)), 3-chloro-1, 1, 2-trifluoro-3-peroxy-1-propene (formula (E)), (E, Z) -1-chloro-2, 3, 3-trifluoro-3-peroxy-1-propene (formula (F)), and the like.
[ solution 1]
[ solution 2]
[ solution 3]
[ solution 4]
[ solution 5]
[ solution 6]
The amount of 3-chloro-2- (difluoromethyl) -2-fluoroethylene oxide, 2-difluoroacetyl fluoride and formyl chloride can be determined by analyzing them with a gas chromatograph. The quantification of hydroperoxides having a structure of-O-H, such as (E, Z) -1-chloro-2, 3, 3-trifluoro-1-peroxy-1-propene, 3-chloro-1, 1, 2-trifluoro-3-peroxy-1-propene, and (E, Z) -1-chloro-2, 3, 3-trifluoro-3-peroxy-1-propene, is carried out by sodium iodide titration and sodium thiosulfate back titration represented by the following reaction formulae [2] and [3 ]. 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]
The titration and back titration described above were specifically performed as follows. About 50mL of a sample solution containing hydroperoxide (ROOH) was mixed with about 40mL of an acetone solution and about 2.5 mass% of sodium iodide (NaI), and further, about 50mL of cold water was additionally mixedBy the reaction formula [2]Iodine (I) produced as shown 2 ) The mixture was colored yellow. The absence of coloration at this time is determined to be equal to or less than the lower limit of hydroperoxide detection. In the case of coloration, 0.01mol/L (0.01N) sodium thiosulfate (Na) is used 2 S 2 O 3 ) The aqueous solution performs back titration on the mixture until the coloration disappears. The quantitative value of hydroperoxide was determined by the following calculation formula using the experimental value of the titration.
Hydroperoxide [ ppm by mass ]
＝{Na 2 S 2 O 3 Consumption of aqueous solution [ mL]×Na 2 S 2 O 3 Molar concentration [ mol/mL]Molecular weight of x (1/2). times.ROOH } per weight of sample solution [ g]×10 6
When the purification composition contains an oxide, the content of the oxide in the purification composition is preferably 0.1% by mass or less, more preferably 0.05% by mass or less, and still more preferably 0.01% by mass or less, relative to the total amount of the purification composition, from the viewpoint of the removal efficiency of the impurity (a).
(HCFC-244ca)
HCFC-244ca is used, for example, as a raw material for producing 1233 yd. At this time, HCFC-244ca was included in the purification composition as an unreacted raw material. When HCFC-244ca is contained in the purification composition, the content of HCFC-244ca in the purification composition 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, from the viewpoint of the efficiency of removing the impurity (A).
[ solid adsorbent ]
The solid adsorbent of the present embodiment adsorbs 1 or more compounds selected from water, 1-chloro-3, 3-difluoro-1-propyne, oxides, and HCFC-244 ca. Examples of the solid adsorbent include activated carbon, zeolite, silica, and alumina. The solid adsorbent may be used alone in 1 kind, or in combination of 2 or more kinds.
The solid adsorbent is preferably an adsorbent which has been subjected to a heat treatment in advance with a dry gas at 100 to 400 ℃ before being brought into contact with the purification composition, or a catalyst which has been subjected to a heat treatment under reduced pressure. Thereby, the adsorption performance of the impurity (a) can be improved.
(activated carbon)
Examples of the activated carbon used in the present embodiment include activated carbons obtained by carbonizing and activating raw materials of activated carbons such as wood, wood flour, coconut shell, and pulp, バカス, syrup, peat, lignite (japanese: dead coal), lignite (japanese: brown coal), bituminous coal, anthracite, petroleum distillation residue components, petroleum pitch, coke, coal tar, and the like, plant-based or fossil-based materials, phenol resins, vinyl chloride resins, vinyl acetate resins, melamine resins, urea resins, resorcinol resins, celluloid, epoxy resins, polyurethane resins, polyester resins, acrylic resins, polyamide resins, and the like, synthetic rubbers such as polybutene, polybutadiene, polychloroprene, and the like, other synthetic woods, and synthetic pulp. Of these activated carbon materials, coconut shell is preferably used because it has high adsorption ability for the impurity (a).
The activated carbon used in the present embodiment was measured by a nitrogen adsorption method at-196 ℃ (ASAP 2405 manufactured by Micromeritics) in view of excellent adsorption performance of the impurity (a). The specific surface area is preferably 600m as pore characteristics 2 /g～2500m 2 G, more preferably 1000m 2 /g～1600m 2 The average pore diameter is preferably 1.6 to 3.5nm, more preferably 1.7 to 2.0 nm. The pore volume is preferably 0.25 to 1.5mL/g, more preferably 0.3 to 1.0 mL/g.
Similarly, from the viewpoint of excellent adsorption performance of the impurity (a), the dry weight loss is 5.0 mass% or less, preferably more than 0 mass% and 5.0 mass% or less, and the burned residual component is preferably 5.0 mass% or less as a general physical property value of the activated carbon used in the present embodiment measured by the JIS K1474 test method. The packing density is preferably 0.25 to 0.85g/mL, more preferably 0.35 to 0.60 g/mL. The pH is preferably 4.0 to 12.0, more preferably 5.0 to 11.0. The acetone adsorption performance is preferably 14.0 mass fraction% to 41.0 mass fraction%, more preferably 25.0 mass fraction% to 39.0 mass fraction%. The iodine adsorption performance is preferably 600mg/g to 2600mg/g, and more preferably 900mg/g to 1600 mg/g. The hardness is preferably 90.0 mass fraction% to 100.0 mass fraction%.
The shape of the activated carbon used in the present embodiment may be, for example, a formed carbon having a length of about 2mm to 10mm, a pulverized carbon having a size of about 4 mesh to 50 mesh, a granular carbon, etc., and from the viewpoint of activity, a pulverized carbon having a size of about 4 mesh to 50 mesh, or a formed carbon having a length of 2mm to 5mm is preferable. Among these, pulverized activated carbon is preferable, and particularly pulverized coconut shell activated carbon is preferable from the viewpoint of economic advantage. As the activated carbon, commercially available products can be used, and activated carbon produced by a known method can also be used. Further, as the activated carbon, activated carbon subjected to pretreatment such as acid treatment, heat treatment, steam treatment, or the like 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]
(wherein x + y is 12, and x: y is 4: 6-8: 2.)
K x Na y [(AlO 2 ) 86 (SiO 2 ) 106 ]·276H 2 O…………[5]
(wherein x + y 86, x: y 4: 6-8: 2.)
Examples of the zeolite used in this embodiment include zeolites 3A, 4A and 5A. The zeolites 3A, 4A and 5A are synthetic zeolites having a fine pore diameter of 0.25nm to 0.45 nm.
The zeolite 3A of the present embodiment is a synthetic zeolite having a pore diameter of 0.28nm ± 0.03 nm. Wherein the synthetic zeolite 3A is capable of passing molecules having an effective diameter of up to 0.3nm due to the expansion and movement energy of the molecules entering the pores at a usual operation temperature.
The zeolite 4A of the present embodiment is a synthetic zeolite having a pore diameter of 0.35nm ± 0.03 nm.
The zeolite 5A of the present embodiment is a synthetic zeolite having a pore diameter of 0.42nm ± 0.03 nm.
Examples of the type a synthetic zeolite include those labeled with 3A, 4A and 5A. Commercially available products include molecular sieves (Japanese: モレキュラーシーブ)3A, 4A, and 5A (trade name of UNION SHOWA K.K. (ユニオン) SHOWA K.K.). Further, a commercially available product of X-type synthetic zeolite is a molecular sieve 13X. In addition, in addition to zeolite 3A, 4A or 5A, molecular sieve 13X may also be used in combination. The pore diameter of the solid adsorbent can be measured by a constant volume gas adsorption method. The adsorbed gas used in the above constant volume gas adsorption method may, for example, be N 2 、CO 2 、CH 4 、H 2 Ar, and the like.
(silica)
In the present embodiment, the silica is mainly composed of SiO 2 A compound of chemical composition (c). Examples of the silica include porous synthetic silica gel, mesoporous silica, and silica alumina. The silica may be used alone in 1 kind, or in combination of 2 or more kinds.
The shape of the silica used as the solid adsorbent may, for example, be in the form of powder, fine particles, granules or films. The shape of the silica can be appropriately selected depending on the reaction method. The shape of the silica is preferably in the form of powder or fine particles from the viewpoint of the adsorption property of the impurity (a). Among them, fine particulate silica is easily handled because it is uniformly dispersed in a liquid purification composition to form a dispersion. In addition, the fine particulate silica easily forms an adsorption layer described later in the reactor.
The porous synthetic silica gel used in the present embodiment is a silica gel having pores. The shape of the porous synthetic silica gel may be a pulverized non-spherical shape or a spherical shape, and is preferably a spherical shape in view of high strength and easy recycling. The "spherical shape" includes not only a spherical shape but also a slightly deformed spherical shape such as an elliptical sphere. The "spherical shape" 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 to 10000. mu.m, more preferably 1 to 5000. mu.m. The average pore diameter of the spherical porous synthetic silica gel is preferably 0.5 to 100nm, more preferably 2 to 50 nm. The specific surface area of the spherical porous synthetic silica gel is preferably 10m 2 /g～10000m 2 G, more preferably 30m 2 /g～1000m 2 (ii) in terms of/g. When the amount is outside these ranges, the content of the effective particles and pores may be reduced, the reaction rate may be reduced, or side reactions may proceed.
The porous synthetic silica gel is easily available as a commercially available product and can be synthesized by a known method. Further, the porous synthetic silica gel may be subjected to a pretreatment such as an activation treatment. For example, commercially available products of porous synthetic silica gel include silica gel (シリカゲル)40 and silica gel 60, which are commonly used as a support for a chromatograph, and spherical silica manufactured by Wakosil C-200 and Wakosil C-300, manufactured by pure Guangdong chemical Co., Ltd (Seki Baoding chemical Co., Ltd.), which are manufactured by pure Guangdong chemical Co., Ltd (Kayaki ).
In the present specification, the average particle size is a value of 50% average particle size on a weight basis as measured by a sieving method prescribed in JIS Z8801. The specific surface area can be N 2 、CO 2 、CH 4 、H 2 Ar and the like were measured by a gas adsorption method.
The mesoporous silica has uniform and regular mesopores (pores having a diameter of 2 to 50 nm) and mainly contains SiO 2 Inorganic matter of chemical composition (1). The shape of the mesoporous silica may, for example, be spherical, powdery, fine particulate or film-like. Among them, spherical fine particles are more preferable in terms of large specific surface area, high strength, easy recovery and use, and easy industrial production. The pore diameter of the mesoporous silica is preferably 2nm to 50nm, more preferably 2nm to 10 nm. If the pore diameter of the mesoporous silica is less than 2nm, the diffusion rate of the purification composition into the mesoporous silica is low, and the adsorption performance may be lowered. On the other hand, pores of mesoporous silicaIf the diameter is larger than 50nm, the purification composition may not be sufficiently contacted with the mesoporous silica, and high selectivity and yield may not be obtained.
The BET specific surface area of the mesoporous silica is preferably 10m 2 /g～3000m 2 A/g, more preferably 50m 2 /g～3000m 2 (ii) in terms of/g. Such mesoporous silica having BET specific surface area can be easily produced, and can be efficiently brought into contact with a purification composition to effectively adsorb the impurity (a).
The average particle diameter of the mesoporous silica is preferably 0.2 to 10000. mu.m, more preferably 1 to 5000. mu.m.
Typical examples of the mesoporous silica include 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 can be obtained and used in a commercially available manner. Alternatively, it can be synthesized by a known method.
Silica alumina is Silica (SiO) 2 ) And alumina (Al) 2 O 3 ) The composite oxide as the main component may be a crystalline oxide or an amorphous oxide. The silica alumina preferably contains silica and alumina in a total amount of 95 mass% or more and a silica content of 50 mol% or more.
The shape of the silica alumina may, for example, be spherical, powdery, fine particulate or film-like. Among them, spherical fine particles are preferable in terms of large specific surface area, high strength, easy recovery and use, and easy industrial production.
The average particle diameter of the spherical fine silica alumina is preferably 0.2 to 20000 μm, more preferably 1 to 10000 μm. The average pore diameter of the silica alumina of the spherical fine particles is preferably 1nm to 100nm, more preferably 2nm to 50 nm. The specific surface area of the spherical fine particles of silica alumina is preferably 10m 2 /g～10000m 2 A ratio of/g, more preferably 30m 2 /g～1000m 2 (ii) in terms of/g. The silica alumina of the spherical fine particles having the above average particle diameter and specific surface area can be easily produced. In addition, if it is the above-mentionedThe average particle diameter or the specific surface area makes the diffusion rate of the purification composition high and the adsorption performance of the impurity (A) excellent.
Silica alumina is readily available as a commercially available product and can be synthesized by known methods. Further, the silica alumina may be subjected to pretreatment such as activation treatment as needed.
Examples of commercially available silica alumina include silica alumina 308 manufactured by Fuji SILYSIA Chemicals K.K. (Fuji シリシア chemical Co.), N633HN, N631HN, N633L and N631L manufactured by Riji CATALYST K.K., Al-MCM-41 and Al-MSU-F manufactured by Sigma Aldrich (シグマアルドリッチ Co.).
(aluminum oxide)
The alumina is mainly Al 2 O 3 A compound of chemical composition (c). As the alumina, activated alumina is preferable. Activated alumina is an inorganic porous body, and is an alumina of a metastable phase in the process of converting from aluminum hydroxide to α -alumina, which is a high-temperature stable phase. Since the large specific surface area is excellent in adsorption performance, the activated alumina is preferably one in the range from amorphous to γ -alumina.
The shape of the activated alumina is preferably a molded body such as a sphere, a cylinder, a rectangular column, a sheet, a hollow cylinder, or a honeycomb, and a granular material having a particle diameter of 3mm to 8mm is preferable in terms of easy handling and reduction of pressure loss at the time of solid-gas contact as much as possible.
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 therebetween. It is considered that, among these pores, the micropores physically adsorb the impurity (a), and the mesopores and macropores moderate the diffusion rate 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 diameters and volumes of the mesopores and macropores in the activated alumina can be adjusted by adjusting the kind of raw material and the molding conditions in the production of the activated alumina.
Excellent in adsorption from the impurity (A)From the viewpoint of good efficiency, the BET specific surface area of the activated alumina is preferably 50m 2 /g～350m 2 G, more preferably 100m 2 /g～350m 2 (ii) in terms of/g. The average pore diameter of the activated alumina as measured by a nitrogen adsorption method is preferably 5 to 200 angstroms, more preferably 10 to 150 angstroms. The pore volume of the activated alumina is preferably 0.1 to 0.8mL/g, more preferably 0.2 to 0.5 mL/g.
(method of contacting solid adsorbent with purification composition)
In the production method of the present embodiment, the impurity (a) in the purification composition is adsorbed to the solid adsorbent and removed by bringing the purification composition containing 1233yd and the impurity (a) into contact with the solid adsorbent.
The purification composition when contacted with the solid adsorbent may be either a gas (gaseous) or a liquid (liquid). In the production method of the present embodiment, when 2 or more kinds of solid adsorbents are used in combination, the order of contacting the solid adsorbents is not particularly limited. For example, the purification composition may be contacted with 2 or more kinds of solid adsorbents in sequence, or 2 or more kinds of solid adsorbents may be mixed and simultaneously contacted. In the case of sequential contact, the solid adsorbent used may be contacted with the purification composition and the solid adsorbent by the contact method described later.
Hereinafter, a method using the composition for purification in a gaseous state will be described as an example. In this method, for example, a solid adsorbent is charged into a reactor to form an adsorption layer, and a gaseous purification composition containing 1233yd is passed through the adsorption layer, whereby the solid adsorbent can be brought into contact with the purification composition. The solid adsorbent according to this method may be contacted with the purification composition in a batch manner or a continuous manner.
The packing density of the solid adsorbent in the adsorption layer is preferably 0.1g/cm 3 Above, more preferably 0.25g/cm 3 The above. If the packing density of the solid adsorbent is not less than the lower limit, the packing amount of the solid adsorbent per unit volume becomes large, and the treatment amount of the purification composition in a gaseous state can be increased, whereby the effect of removing impurities (A) other than 1233yd can be enhancedThe rate is improved. The adsorption layer may be 1 layer or 2 or more layers. When the number of the adsorption layers is 2 or more, these adsorption layers may be arranged in parallel or in series.
The temperature of the adsorption layer at the time of contact is preferably 60 to 100 ℃ and more preferably 70 to 90 ℃ which is not less than the boiling point of 1233yd in order to maintain the purification composition in a gaseous state. If the temperature of the adsorption layer is not lower than the lower limit, the efficiency of removing the impurity (a) by the solid adsorbent is improved. If the temperature of the adsorption layer is not higher than the upper limit, the energy required for cooling the purified composition is less, and the equipment and the like are simple.
The pressure (gauge pressure, hereinafter the same applies) in the reactor at the time of contact is preferably 10kPa to 500kPa, more preferably 90kPa to 300 kPa. If the pressure is not lower than the lower limit, the efficiency of removing the impurities (A) is improved. If the pressure is not more than the upper limit, the operability is good and the facility and the like can be easily realized.
The contact time between the purification composition in the gaseous state flowing through the adsorption layer and the adsorption layer is preferably 1 second to 1000 seconds, and more preferably 3 seconds to 300 seconds. When the contact time between the gaseous purification composition and the adsorption layer is not less than the lower limit, the removal efficiency of the impurity (a) is improved. If the contact time between the purification composition in the gaseous state and the adsorbent layer is not more than the upper limit, the purification of the purification composition can be completed using a small adsorbent layer, and the facility and the like are simple. In the method of passing the purification composition containing 1233yd through the adsorption layer, the contact time corresponds to the retention time of the purification composition in the reactor, and can be controlled by adjusting the supply amount (flow rate) of the purification composition to the reactor. The same applies to the case of using a liquid purification composition described later.
In addition, from the viewpoint of removal efficiency, the total amount of impurities (a) contained in the gaseous purification composition flowing through the adsorption layer is preferably 0.05 parts by mass or less, and more preferably 0.02 parts by mass or less, relative to 1 part by mass of the solid adsorbent in the adsorption layer. That is, in the method using the composition for gaseous purification, it is preferable to adjust the amount of the composition for gaseous purification to be contacted with the solid adsorbent so that the ratio of the impurity (a) to the solid adsorbent is not more than the above upper limit value, and then to perform the contact.
The reactor used for contacting the purification composition gas with the solid adsorbent may be any reactor capable of forming an adsorption layer by filling the solid adsorbent. Examples of the material of the reactor include glass, iron, nickel, alloys containing these components as main components, and fluorine resins such as tetrafluoroethylene-perfluoro (alkyl vinyl ether) copolymer (PFA).
Next, a method of using the liquid purification composition will be described. In this method, as in the case of the method using a gaseous purification composition, a method can be employed in which an adsorption layer is formed in a reactor and a liquid purification composition containing 1233yd is passed through the adsorption layer. In addition, a method of immersing the solid adsorbent in the purification composition in a reactor containing the solid adsorbent, and mixing and stirring the resultant as necessary can be employed. The solid adsorbent according to these methods may be contacted with the purification composition in a batch manner or a continuous manner.
When the purification composition is contacted with the solid adsorbent in a liquid state, the purification composition may be adjusted to a temperature of a boiling point or lower at normal pressure to form a liquid state. In addition, the purification composition may be dissolved in a solvent to form a liquid state. By using a solvent having a boiling point different from that of 1233yd as the solvent used in this case, the solvent can be easily removed from the purified composition by a method such as distillation.
The temperature in the reactor when the solid adsorbent is contacted with the purification composition is preferably-30 to 70 ℃ and more preferably 10 to 40 ℃. When the temperature in the reactor is not lower than the lower limit, the removal rate of impurities other than 1233yd is increased. If the temperature in the reactor is not higher than the upper limit, the amount of energy required for cooling the purified composition is small, and the facilities and the like are simple.
The pressure in the reactor when the solid adsorbent is contacted with the purification composition is preferably 0kPa to 200kPa, more preferably 100kPa to 150 kPa. If the pressure is not lower than the lower limit, the removal rate of impurities other than 1233yd is increased. If the pressure is not more than the upper limit, the operability is good and the facility and the like can be easily realized.
In the method of flowing the purification composition containing 1233yd through the adsorption layer, the contact time between the purification composition in a liquid state flowing through the adsorption layer and the adsorption layer is preferably 1 second to 1000 seconds, and more preferably 3 seconds to 300 seconds. When the contact time between the liquid purification composition and the adsorption layer is not less than the lower limit, the removal efficiency of the impurity (a) is improved. If the contact time between the liquid purification composition and the adsorbent layer is not more than the upper limit, the purification of the composition can be completed using a small adsorbent layer, and the equipment and the like are simple.
The packing density of the solid adsorbent in the adsorption layer and the configuration of the adsorption layer are preferably the same as those in the method using the gaseous purification composition.
In the method of impregnating the solid adsorbent with the purification composition in the reactor containing the solid adsorbent, the contact time of the liquid purification composition with the solid adsorbent in the reactor is preferably 1 hour to 100 hours, and more preferably 3 hours to 60 hours. When the contact time between the liquid purification composition and the solid adsorbent is not less than the lower limit, the removal efficiency of the impurity (a) is improved. If the contact time between the liquid purification composition and the solid adsorbent is not more than the upper limit, the purification of the purification composition can be completed using a small amount of the solid adsorbent, and the facilities and the like are simple.
In the method of impregnating the solid adsorbent in the purification composition in the reactor, after purification of the purification composition, the purified composition may be separated from the solid adsorbent by settling or filtration.
In addition, from the viewpoint of improving the removal efficiency of the impurity (a), the total amount of the impurity (a) contained in the liquid purification composition that is brought into contact with the solid adsorbent is preferably 0.05 parts by mass or less, and more preferably 0.02 parts by mass or less, relative to 1 part by mass of the solid adsorbent. That is, in the method using a liquid purification composition, it is preferable to adjust the liquid amount of the purification composition to be brought into contact with the solid adsorbent so that the ratio of the impurity (a) to the solid adsorbent is not more than the upper limit value, and then to bring the impurity (a) into contact with the solid adsorbent.
The reactor used for contacting the liquid purification composition with the solid adsorbent may be, for example, a reactor capable of accommodating the solid adsorbent or a reactor capable of forming an adsorption layer composed of the solid adsorbent. Examples of the material of the reactor include glass, iron, nickel, alloys containing these components as main components, and fluorine resins such as tetrafluoroethylene-perfluoro (alkyl vinyl ether) copolymer (PFA). The reactor for mixing and contacting the mixed liquid with the solid adsorbent may, for example, be a reactor capable of contacting the purification composition in a liquid state with the solid adsorbent at a desired temperature and pressure, and may, for example, be an autoclave.
(composition after purification)
In general, the compound that is easily adsorbed by the solid adsorbent differs depending on the composition of the composition to be purified and the type of the solid adsorbent (material composition and pore size). In the present embodiment, which is the object of purification, a composition containing 1233yd and 1 or more compounds selected from the group consisting of water, 1-chloro-3, 3-difluoro-1-propyne, an oxide and HCFC-244ca, for example, water is easily adsorbed to zeolite, preferably zeolite 3A or zeolite 4A. In addition, water is also readily adsorbed to alumina and silica. Therefore, in the purification of the present embodiment, the 1233yd can be purified by contacting the composition for purification containing 1233yd and water with alumina, silica, or zeolite (particularly, zeolite 3A or 4A) as a solid adsorbent, thereby selectively removing the water in the composition.
The oxide in the purification composition is easily adsorbed to activated carbon or alumina. Therefore, in the purification of the present embodiment, 1233yd can be produced by contacting a purification composition containing 1233yd and an oxide with activated carbon or alumina as a solid adsorbent to selectively remove the oxide.
In addition, 1-chloro-3, 3-difluoro-1-propyne in the purification composition is readily adsorbed to activated carbon, silica and alumina. Therefore, 1233yd can be produced by efficiently removing 1-chloro-3, 3-difluoro-1-propyne from a purification composition by contacting the purification composition containing 1233yd and 1-chloro-3, 3-difluoro-1-propyne with activated carbon, silica or alumina as a solid adsorbent.
In addition, HCFC-244ca in the purification composition is easily adsorbed to activated carbon, alumina, and zeolites 4A and 5A. Therefore, by using activated carbon, zeolite 4A or zeolite 5A as a solid adsorbent and contacting with a purification composition containing 1233yd and HCFC-244ca, it is possible to efficiently remove HCFC-244ca from the purification composition to produce 1233 yd.
In this manner, by using 1 kind of solid adsorbent alone or 2 or more kinds of solid adsorbents in combination, the impurity (a) contained in the purification composition can be removed to a desired degree of the desired compound.
By removing the impurity (a) contained in the purification composition by the production method of the present embodiment, a composition having a reduced content of the impurity (a) can be obtained.
The content of 1233yd in the composition purified by the production method of the present embodiment is preferably 90% by mass or more, more preferably 95% by mass or more, and still more preferably 99% by mass or more. The water content in the purified composition is preferably 0.005% by mass or less, and the content of 1-chloro-3, 3-difluoro-1-propyne is preferably 0.001% by mass or less, more preferably 0.0005% by mass or less, and still more preferably 0.0003% by mass or less. The content of HCFC-244ca in the purified composition is preferably 0.1% by mass or less, more preferably 0.058% by mass or less. If the content of each component is not more than the upper limit, various properties can be exhibited in various applications. The content of the oxide in the purified composition is preferably 5 mass ppm or less. If the content of the oxide is not more than the upper limit, the stability of the solvent composition can be sufficiently prevented from being lowered. If the content of the oxide is not more than the upper limit, the content may not be decreased to the limit of 0 mass ppm. The content of the oxide in the purified composition is preferably 1 mass ppm or more, and more preferably 2 mass ppm or more. When the content is not less than the lower limit, oxidation of 1233yd is suppressed, and the solvent composition is excellent in stability.
< embodiment 2 >
The method for producing 1233yd according to embodiment 2 of the present invention includes a step of producing a purification composition containing 1233 yd.
In the production method of the present embodiment, a reaction product obtained in the production step of 1233yd shown in (I) or (II), or a mixed composition obtained by removing an acidic substance or the like from the reaction product can be used as the purification composition. In this manner, the purification as described in embodiment 1 above can be performed on the purification composition to efficiently remove the impurity (a) from the composition containing 1233yd and the impurity (a).
(I) Method for making HCFC-244ca react with hydrogen fluoride in gas phase under nitrogen flow by using chromic oxide as catalyst
A raw material composition containing HCFC-244ca and hydrogen fluoride was reacted in a vapor phase in a reactor having a catalyst layer filled with chromium oxide to produce a composition containing 1233 yd.
In the vapor-phase catalytic reaction between HCFC-244ca and hydrogen fluoride, a reaction product containing 1233yd and an acidic substance such as hydrogen chloride can be obtained. Then, the acidic substance contained in the reaction product is removed by alkali washing or the like, whereby a mixed composition can be obtained. Examples of the compound other than 1233yd contained in the mixed composition may include water, 1-chloro-3, 3-difluoro-1-propyne, HCFC-245ca, and 2,3, 3-trifluoropropene (H) in addition to HCFC-244ca as an unreacted raw material 2 C＝CF-CHF 2 ) 1,2,3, 3-tetrafluoropropene (HFC ═ CF-CHF) 2 ) And oxides and the like.
The purification as described in embodiment 1 above can be carried out using the reaction product or mixed composition obtained in this way as a purification composition, whereby the impurity (a) in the purification composition can be efficiently removed. The reaction product, the mixed composition, and other components other than 1233yd contained in the purified composition may be removed to a desired extent by a known method such as distillation. In addition, HCFC-244ca separated from 1233yd by the solid adsorbent is released from the solid adsorbent and recovered, whereby it can be recycled as a part of the raw material.
(II) method for dehydrofluorination of HCFC-244ca at 40-80 ℃ by using potassium hydroxide or sodium hydroxide as reactant
HCFC-244ca is dehydrofluorinated in an aqueous potassium hydroxide solution or aqueous sodium hydroxide solution at a temperature of 40 ℃ to 80 ℃ to produce a composition containing 1233 yd. In the above reaction, the dehydrofluorination reaction is preferably carried out 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 aqueous potassium hydroxide solution or aqueous sodium hydroxide solution is preferably 1 to 3 times the molar number of HCFC-244 ca.
In the synthesis method, HCFC-244ca is subjected to dehydrofluorination reaction at a temperature of 40-80 ℃ by using potassium hydroxide or sodium hydroxide as a reactant, and a reaction product containing 1233yd can be obtained. Examples of the compound other than 1233yd contained in the reaction product include compounds such as water, 1-chloro-3, 3-difluoro-1-propyne, and an oxide, in addition to the unreacted HCFC-244 ca.
The reaction product obtained in this way is used as a purification composition, and purification as described in embodiment 1 above is performed, whereby the impurity (a) in the purification composition can be efficiently removed. The reaction product and other components other than 1233yd contained in the purified composition can be removed to a desired extent by a known method such as distillation. In addition, HCFC-244ca separated from 1233yd by the solid adsorbent is released from the solid adsorbent and recovered, whereby it can be recycled as a part of the raw material.
Examples
The present invention will be described below with reference to examples, but the present invention is not limited to these examples.
(analysis method)
The content (content ratio) of the components other than water and hydroperoxide in the composition to be analyzed was analyzed by gas chromatography. DB-1301 (60 m length 250 u m diameter 1 u m thick, Agilent technologies (アジレント, テクノロジー) as a column. The water content was analyzed by a karl fischer moisture meter and the hydroperoxide content was analyzed by the hydroperoxide assay method described above.
Further, the analysis results of the gas chromatography, the karl fischer moisture meter and the hydroperoxide measurement method were used to determine the proportion (mass%) of 1-chloro-3, 3-difluoro-1-propyne, the proportion (mass%) of water, the proportion (mass%) of oxide and the proportion (mass%) of HCFC-244ca with respect to the total amount of the composition to be analyzed.
In addition, the content of the oxide is the total amount of the analysis results of the above-mentioned gas chromatography and hydroperoxide measuring method.
(preparation example: preparation of 1233yd)
2000g of HCFC-244ca was used as a raw material, 19.9g of tetra-n-butylammonium chloride was added thereto, the reaction temperature was maintained at 50 ℃, and 2792g of a 40 mass% aqueous solution of potassium hydroxide was added dropwise over 30 minutes. The reaction was continued for 52 hours, and the organic phase and the aqueous phase were separated to recover the organic phase. The recovered organic phase was subjected to crude distillation to recover a fraction, thereby obtaining a composition (purification composition) containing 1233yd, water, 1-chloro-3, 3-difluoro-1-propyne and an oxide.
(example 1)
The content of the oxide in the 1233 yd-containing purification composition obtained in the production example was determined by the gas chromatography and the hydroperoxide measurement method, and as a result, the content of the oxide was 20 mass ppm in 3-chloro-2- (difluoromethyl) -2-fluoroethylene oxide and the content of the hydroperoxide was 19 mass ppm, and the total content of the oxide was 39 mass ppm. Therefore, to the above-mentioned purification composition containing an oxide, 1 mass% of 1233yd activated carbon (manufactured by Serachem corporation, セラケム Corp.) having a coconut-shell type pulverized activated carbon product name of Fuji charcoal B-CW was added based on 1kg of the purification composition, and the mixture was allowed to stand at room temperature for 48 hours. After 48 hours, the activated carbon was separated from 1233yd and the oxide content was measured, whereby 0 mass ppm of 3-chloro-2- (difluoromethyl) -2-fluoroethylene oxide and 2.2 mass ppm of hydroperoxide were obtained, and the total was 2.2 mass ppm.
(example 2)
To the purification composition containing 39 mass ppm of the oxide, 1 mass% of activated alumina (manufactured by Fuji corporation, product name PSG-D25) was added with respect to 1kg of 1233yd in the purification composition, and the mixture was allowed to stand at room temperature for 48 hours. After 48 hours, the content of the oxide was measured by separating active alumina from 1233yd, and as a result, the content of 3-chloro-2- (difluoromethyl) -2-fluoroethylene oxide was 0 mass ppm and the content of hydroperoxide was 3.2 mass ppm, which was 3.2 mass ppm in total.
As is clear from examples 1 and 2, by bringing the purification composition containing 1233yd into contact with activated carbon or activated alumina, oxides can be effectively removed from the purification composition.
(example 3)
The composition of the 1233 yd-containing purified composition obtained in the production examples, except for the oxide, was analyzed, and as a result, 1233yd, water, 1-chloro-3, 3-difluoro-1-propyne, and HCFC-244ca were contained in the compositions shown in table 1. 1233yd having the composition ratio shown in Table 1 was charged into a 1L polypropylene container with a lid, and 1 mass% of activated carbon (coconut-shell-type pulverized activated carbon, product name: Fuji charcoal B-CW, manufactured by Serachem corporation) was added to 1kg of 1233yd in the purification composition, and the mixture was allowed to stand at room temperature for 48 hours. After 48 hours, the activated carbon was separated from the purification composition and analyzed for compositions other than oxides, resulting in the compositions shown in table 1.
(example 4)
The treatment was carried out in the same manner as in example 3 except that activated alumina (manufactured by Fuji corporation, activated alumina, product name PSG-D25) was used in place of activated carbon. After the treatment, activated alumina was separated from the purification composition and analyzed for compositions other than oxides, resulting in compositions shown in table 1.
(example 5)
The treatment was carried out in the same manner as in example 3 except that zeolite 3A (trade name: molecular sieve 3A, manufactured by UNION SHOWA CO., LTD.) was used in place of activated carbon. After the treatment, zeolite 3A was separated from the purification composition and analyzed for compositions other than oxides, resulting in compositions shown in table 1.
(example 6)
The treatment was carried out in the same manner as in example 3 except that zeolite 4A (trade name: molecular sieve 4A, manufactured by UNION SHOWA CO., LTD.) was used in place of activated carbon. After the treatment, zeolite 4A was separated from the purification composition and analyzed for compositions other than oxides, resulting in compositions shown in table 2.
(example 7)
The treatment was carried out in the same manner as in example 3 except that zeolite 5A (product name: molecular sieve 5A, manufactured by UNION SHOWA CO., LTD.) was used in place of activated carbon. After the treatment, zeolite 5A was separated from the purification composition and analyzed for compositions other than oxides, resulting in compositions shown in table 2.
(example 8)
The treatment was carried out in the same manner as in example 3 except that a silica gel (product name: spherical silica gel (particle diameter: 63 to 210 μm), manufactured by Kanto chemical Co., Ltd.) was used in place of the activated carbon. After the treatment, the silica gel was separated from the purification composition and analyzed for compositions other than oxides, resulting in compositions shown in table 2.
[ Table 1]
[ Table 2]
From examples 3 to 8, it was found that by bringing the purification composition containing 1233yd into contact with activated carbon, alumina, zeolite 3A, zeolite 4A, zeolite 5A and silica gel, water, 1-chloro-3, 3-difluoro-1-propyne and HCFC-244ca can be efficiently removed from the purification composition. In particular, it is found that the use of alumina, zeolite 3A, zeolite 4A, zeolite 5A or silica gel is effective in removing water from the purification composition, and the use of activated carbon, alumina, zeolite 5A or silica gel is effective in removing 1-chloro-3, 3-difluoro-1-propyne from the purification composition. Further, it is found that the use of activated carbon, alumina, zeolite 4A and zeolite 5A is effective in removing HCFC-244 ca.
Possibility of industrial utilization
By the process for producing 1-chloro-2, 3, 3-trifluoropropene of the present invention, water, 1-chloro-3, 3-difluoro-1-propyne, an oxide and HCFC-244ca can be efficiently removed from a composition containing 1-chloro-2, 3, 3-trifluoropropene and 1 or more compounds selected from the group consisting of water, 1-chloro-3, 3-difluoro-1-propyne, and an oxide and HCFC-244 ca.
Further, according to the production method of the present invention, by purifying the 1-chloro-2, 3, 3-trifluoropropene, it is possible to efficiently produce the 1-chloro-2, 3, 3-trifluoropropene by removing water, 1-chloro-3, 3-difluoro-1-propyne, an oxide and HCFC-244ca from a composition containing the 1-chloro-2, 3, 3-trifluoropropene and 1 or more compounds selected from the group consisting of water, 1-chloro-3, 3-difluoro-1-propyne, an oxide and HCFC-244 ca.
Claims (2)
- A process for producing 1-chloro-2, 3, 3-trifluoropropene, which comprises contacting a composition comprising 1-chloro-2, 3, 3-trifluoropropene and at least 1 compound selected from the group consisting of 1-chloro-3, 3-difluoro-1-propyne, an oxide and 3-chloro-1, 1,2, 2-tetrafluoropropane with a solid adsorbent to remove the compound contained in the composition,when the composition contains an oxide, the solid adsorbent contains at least 1 selected from the group consisting of activated carbon and alumina to remove the oxide from the composition, wherein the oxide is selected from the group consisting of 3-chloro-2- (difluoromethyl) -2-fluoroethylene oxide, E-form of 1-chloro-2, 3, 3-trifluoro-1-peroxy-1-propene, Z-form of 1-chloro-2, 3, 3-trifluoro-1-peroxy-1-propene, 3-chloro-1, 1, 2-trifluoro-3-peroxy-1-propene, E-form of 1-chloro-2, 3, 3-trifluoro-3-peroxy-1-propene, and mixtures thereof, At least one compound represented by the formula Z of 1-chloro-2, 3, 3-trifluoro-3-peroxy-1-propene,when the composition contains 1-chloro-3, 3-difluoro-1-propyne, the solid adsorbent contains at least 1 selected from the group consisting of activated carbon, silica and alumina to remove the 1-chloro-3, 3-difluoro-1-propyne from the composition,when the composition contains 3-chloro-1, 1,2, 2-tetrafluoropropane, the solid adsorbent contains at least 1 selected from the group consisting of activated carbon, alumina, and zeolite 5A to remove the 3-chloro-1, 1,2, 2-tetrafluoropropane from the composition.
- 2. The process for producing 1-chloro-2, 3, 3-trifluoropropene according to claim 1, further comprising a step of dehydrofluorinating 3-chloro-1, 1,2, 2-tetrafluoropropane to produce a composition comprising 1-chloro-2, 3, 3-trifluoropropene and at least 1 compound selected from the group consisting of 1-chloro-3, 3-difluoro-1-propyne, an oxide and 3-chloro-1, 1,2, 2-tetrafluoropropane.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2016222183 | 2016-11-15 | ||
| JP2016-222183 | 2016-11-15 | ||
| PCT/JP2017/040984 WO2018092780A1 (en) | 2016-11-15 | 2017-11-14 | Method for producing 1-chloro-2, 3, 3-trifluoropropene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109937196A CN109937196A (en) | 2019-06-25 |
| CN109937196B true CN109937196B (en) | 2022-08-16 |
Family
ID=62145562
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201780070437.4A Active CN109937196B (en) | 2016-11-15 | 2017-11-14 | Method for producing 1-chloro-2, 3, 3-trifluoropropene |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP7003934B2 (en) |
| CN (1) | CN109937196B (en) |
| WO (1) | WO2018092780A1 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021085134A1 (en) * | 2019-10-31 | 2021-05-06 | セントラル硝子株式会社 | Composition comprising 1-chloro-2,3,3-trifluoro-1-propene and water, and method for storing composition |
| WO2021132390A1 (en) * | 2019-12-26 | 2021-07-01 | Ａｇｃ株式会社 | Method for producing 1-chloro-2,3,3-trifluoropropene |
| WO2021153681A1 (en) * | 2020-01-31 | 2021-08-05 | Ａｇｃ株式会社 | Solvent composition, cleaning method, and method for producing article with coating film |
| JP2023019285A (en) | 2021-07-29 | 2023-02-09 | 三井・ケマーズ フロロプロダクツ株式会社 | Fluorine-based solvent composition |
| CN115779497A (en) * | 2022-12-07 | 2023-03-14 | 九江中船消防设备有限公司 | 2-bromo-3,3,3-trifluoropropene water removal device |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102164881A (en) * | 2008-09-25 | 2011-08-24 | 中央硝子株式会社 | Process for producing 1,3,3,3-tetrafluoropropene |
| CN102695692A (en) * | 2009-10-15 | 2012-09-26 | 墨西哥化学阿玛科股份有限公司 | Process for purifying (hydro) fluoroalkenes |
| CN105431399A (en) * | 2013-03-15 | 2016-03-23 | 得凯莫斯公司弗罗里达有限公司 | Process for the reduction of alkyne impurities in fluoroolefins |
| WO2016136744A1 (en) * | 2015-02-27 | 2016-09-01 | ダイキン工業株式会社 | Method for producing 1-chloro-2,3,3-trifluoropropene |
| WO2016148957A1 (en) * | 2015-03-19 | 2016-09-22 | Honeywell International Inc. | PROCESS FOR DRYING HCFO-1233zd |
| CN106029615A (en) * | 2014-02-20 | 2016-10-12 | 旭硝子株式会社 | Method for purifying fluid that includes trifluoroethylene, and method for producing trifluoroethylene |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4552246B2 (en) * | 1999-12-28 | 2010-09-29 | 株式会社クレハ | Method for producing purified fluorocarbon or chlorofluorocarbon |
| JP2013241389A (en) * | 2012-04-25 | 2013-12-05 | Asahi Glass Co Ltd | Method for drying fluid containing fluoroolefin, and method for producing fluoroolefin |
| JP6107466B2 (en) * | 2012-06-28 | 2017-04-05 | セントラル硝子株式会社 | Method for purifying trans-1,3,3,3-tetrafluoropropene |
| PT2970058T (en) * | 2013-03-15 | 2024-03-05 | Honeywell Int Inc | Methods for removing halogenated ethylene impurities in 2,3,3,3-tetrafluoropropene product |
-
2017
- 2017-11-14 WO PCT/JP2017/040984 patent/WO2018092780A1/en active Application Filing
- 2017-11-14 JP JP2018551649A patent/JP7003934B2/en active Active
- 2017-11-14 CN CN201780070437.4A patent/CN109937196B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102164881A (en) * | 2008-09-25 | 2011-08-24 | 中央硝子株式会社 | Process for producing 1,3,3,3-tetrafluoropropene |
| CN102695692A (en) * | 2009-10-15 | 2012-09-26 | 墨西哥化学阿玛科股份有限公司 | Process for purifying (hydro) fluoroalkenes |
| CN105431399A (en) * | 2013-03-15 | 2016-03-23 | 得凯莫斯公司弗罗里达有限公司 | Process for the reduction of alkyne impurities in fluoroolefins |
| CN106029615A (en) * | 2014-02-20 | 2016-10-12 | 旭硝子株式会社 | Method for purifying fluid that includes trifluoroethylene, and method for producing trifluoroethylene |
| WO2016136744A1 (en) * | 2015-02-27 | 2016-09-01 | ダイキン工業株式会社 | Method for producing 1-chloro-2,3,3-trifluoropropene |
| WO2016148957A1 (en) * | 2015-03-19 | 2016-09-22 | Honeywell International Inc. | PROCESS FOR DRYING HCFO-1233zd |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2018092780A1 (en) | 2018-05-24 |
| CN109937196A (en) | 2019-06-25 |
| JPWO2018092780A1 (en) | 2019-10-17 |
| JP7003934B2 (en) | 2022-02-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109937196B (en) | Method for producing 1-chloro-2, 3, 3-trifluoropropene | |
| Yaumi et al. | Melamine-nitrogenated mesoporous activated carbon derived from rice husk for carbon dioxide adsorption in fixed-bed | |
| CN103827068B (en) | Use the method that solid absorbent separates alkenyl halide from 2-chloro-1,1,1,2-tetrafluoropropane | |
| CN108368011B (en) | Process for producing hydrofluoroolefin | |
| KR102634564B1 (en) | Method for purifying hexafluorobutadiene | |
| JP2012001495A (en) | Method for purifying 2,3,3,3-tetrafluoropropene | |
| JP2010227936A (en) | Method for removing water from ammonia | |
| US10047026B2 (en) | Process for reducing 1233xf concentration in 244bb | |
| JP5259090B2 (en) | Chloride removal method and chloride absorbent | |
| JP2007229707A (en) | Organic gas adsorbent | |
| KR20180065035A (en) | Removal of fluorinated organics from anhydrous or aqueous hydrochloric acid, a by-product of 1234 YF via 1230 XA process | |
| WO2020026990A1 (en) | Method for producing purified fluorine-containing unsaturated hydrocarbon | |
| US9012712B1 (en) | Adsorption of acid gases | |
| WO2014185321A1 (en) | Purification method for dichloromethane, and production method for difluoromethane using said purification method | |
| JP7331844B2 (en) | Method for producing 1-chloro-2,3,3,4,4,5,5-heptafluoro-1-pentene, and composition | |
| EP3334691B1 (en) | Composition and process for removing chlorides from a gaseous stream | |
| JP6777072B2 (en) | Method for producing hydrofluoroolefin | |
| JP2020044474A (en) | Absorbent for organic halogen compound, method for removing organic halogen compound from hydrocarbon gas using the same, absorption apparatus of halogen compound using the method, and method for manufacturing hydrocarbon gas | |
| CN114746385A (en) | Method for dehydrating fluorine-containing hydrocarbon compound | |
| JP2020040921A (en) | Method for producing 1,3-dichloro-2,3,3-trifluoropropene |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |