CN109937196A - The manufacturing method of the chloro- 2,3,3- trifluoro propene of 1- - Google Patents
The manufacturing method of the chloro- 2,3,3- trifluoro propene of 1- Download PDFInfo
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- CN109937196A CN109937196A CN201780070437.4A CN201780070437A CN109937196A CN 109937196 A CN109937196 A CN 109937196A CN 201780070437 A CN201780070437 A CN 201780070437A CN 109937196 A CN109937196 A CN 109937196A
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- C07C17/25—Preparation of halogenated hydrocarbons by splitting-off hydrogen halides from halogenated hydrocarbons
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Abstract
The present invention provide from contain 1- chloro- 2,3, the composition of 3- trifluoro propene is efficiently removed selected from water, 1- chloro- 3,1 kind or more of compound of the fluoro- 1- propine of 3- bis-, oxide and HCFC-244ca is efficiently to manufacture 1- chloro- 2,3, the manufacturing method of the chloro- 2,3,3- trifluoro propene of the 1- of 3- trifluoro propene.Make containing 1- chloro- 2,3,3- trifluoro propene and be selected from water, 1- chloro- 3, the fluoro- 1- propine of 3- bis-, oxide and 3- chloro- 1,1,2, the composition of at least one kind of compound of 2- tetrafluoropropane is contacted with solid absorbent, the 1- chloro- 2 that the compound contained by the composition is removed, the manufacturing method of 3,3- trifluoro propenes.
Description
Technical field
The present invention is provided from containing the chloro- 2,3,3- trifluoro propene of 1- and selected from water, the fluoro- 1- propine of the chloro- 3,3- bis- of 1-, oxidation
In the composition of object and a kind or more of compound of the chloro- 1,1,2,2- tetrafluoropropane of 3- will except the chloro- 2,3,3- trifluoro propene of 1- with
The manufacturing method for the chloro- 2,3,3- trifluoro propene of 1- that outer impurity removes.
Background technique
Hydrochlorofluorocarbons (HCFC) has a negative impact to ozone layer, therefore plan limits its production.HCFC for example including 3,
The chloro- 1,1,1,2,2- pentafluoropropane (HCFC-225ca) of 3- bis- and the chloro- 1,1,2,2,3- pentafluoropropane (HCFC- of 1,3- bis-
225cb) etc., with the limitation to HCFC, it is expected that developing the compound for substituting above-mentioned HCFC.
An example for substituting the compound of HCFC is the chloro- 2,3,3- trifluoro propene (HClC=CF-CHF of 1-2, HCFO-
1233yd).The chamber effect potential value (GWP) of 1233yd is low, is that can be used for cleaning agent, solvent, refrigerant, foaming agent gentle molten
The compound of glue purposes.
In this regard, patent document 1, which is disclosed, makes chloro- 1,1,2,2- tetrafluoropropane (HCFC- of 3- by catalyst of chromium hydroxide
244ca) under stream of nitrogen gas in gas phase with hydrogen fluoride reaction to manufacture 1,1,2,2,3- pentafluoropropane (HCFC-245ca)
Method.The 1233yd as by-product is generated in this method.Therefore, by recycling the above-mentioned resulting composition of reaction to separate this
The 1233yd contained in composition can obtain the composition containing 1233yd.It will can obtain like this containing 1233yd's
Composition is used for cleaning agent, solvent, refrigerant, foaming agent or aerosol purposes.
But sometimes containing as unreacting material in the composition containing 1233yd obtained by above-mentioned manufacturing method
HCFC-244ca, the fluoro- 1- propine of the chloro- 3,3- bis- of 1-, water, the oxygen in air that generate as by-product in its manufacturing process will
The oxide etc. of 1233yd oxidation and generation.
When the composition for containing 1233yd is used as cleaning agent, solvent, refrigerant, foaming agent or aerosol, contain
If the fluoro- 1- propine of chloro- 3, the 3- bis- of water, 1- comprising high concentration, HCFC-244ca etc., then may in the composition of 1233yd
Lead to the various problems of reliability and aspect of performance.In order to reduce this adverse effect, be preferably reduced as far as containing
The amount of the fluoro- 1- propine of the chloro- 3,3- bis- of water contained in the composition of 1233yd, 1-, HCFC-244ca etc..
In addition, containing when the composition containing 1233yd is used as cleaning agent, solvent, refrigerant, foaming agent or aerosol
If the oxide comprising high concentration in the composition of 1233yd, the life of stability reduction and acidification substance may result in
At the problems such as.To inhibit this adverse effect, it is preferably reduced as far as mixed oxide in the composition containing 1233yd
Amount.
But documents 1 do not record that efficiently to remove chloro- 3, the 3- bis- of water, 1- from the composition containing 1233yd fluoro-
The method of 1- propine and oxide.
Existing technical literature
Patent document
Patent document 1: International Publication No. 1994/014737
Summary of the invention
The technical problems to be solved by the invention
The present invention completed in view of above-mentioned viewpoint, and it is an object of the present invention to provide can efficiently from containing 1233yd and selected from water,
The composition of a kind or more of compound of the fluoro- 1- propine of the chloro- 3,3- bis- of 1-, oxide and HCFC-244ca, which removes, is selected from water, 1-
The manufacturing method of the 1233yd of a kind or more of compound of the fluoro- 1- propine of chloro- 3,3- bis-, oxide and HCFC-244ca.
Technical scheme applied to solve the technical problem
1- of the invention chloro- 2, the manufacturer of 3,3- trifluoro propenes (HCFO-1233yd is also abbreviated as " 1233yd " below)
The feature of method is to make containing 1- chloro- 2,3,3- trifluoro propenes and selected from water, the fluoro- 1- propine of chloro- 3, the 3- bis- of 1-, oxide and 3-
Chloro- 1, the composition of at least one kind of compound of 1,2,2- tetrafluoropropane is contacted with solid absorbent, will be contained by the composition
The compound removes.
1- of the invention chloro- 2, in the manufacturing method of 3,3- trifluoro propenes, the preferably described solid absorbent contains selected from living
Property charcoal, zeolite, silica and aluminium oxide it is at least one kind of.
1- of the invention chloro- 2, in the manufacturing method of 3,3- trifluoro propenes, the preferably described composition contains water, the solid
Adsorbent contains selected from at least one kind of of zeolite, silica and aluminium oxide, to remove the water from the composition.
1- of the invention chloro- 2, in the manufacturing method of 3,3- trifluoro propenes, the preferably described composition contains oxide, described
Solid absorbent contain it is at least one kind of selected from active carbon and aluminium oxide, to remove the oxide from the composition.
In addition, 1- of the invention chloro- 2, in the manufacturing method of 3,3- trifluoro propenes, the preferably described oxide is selected from 3-
Chloro- 2- (difluoromethyl) -2- fluoro ethylene oxide, bis- fluoracyl fluoride of 2,2-, formyl chloride, the fluoro- 1- peroxidating of the chloro- 2,3,3- tri- of 1-
Z formula body, the 3- of the fluoro- 1- peroxidating base -1- propylene of the chloro- 2,3,3- tri- of the E formula body, 1- of base (hydroperoxy) -1- propylene are chloro-
E formula body, the 1- chloro- 2 of the fluoro- 3- peroxidating base -1- propylene of 1,1,2- tri-, the fluoro- 3- peroxidating base -1- propylene of the chloro- 2,3,3- tri- of 1-,
At least one of the Z formula body of the fluoro- 3- peroxidating base -1- propylene of 3,3- tri-.
In addition, 1- of the invention chloro- 2, in the manufacturing method of 3,3- trifluoro propenes, it is chloro- that the preferably described composition contains 1-
3,3- bis- fluoro- 1- propine, the solid absorbent contain selected from at least one kind of of active carbon, silica and aluminium oxide, with from institute
It states composition and removes the fluoro- 1- propine of the chloro- 3,3- bis- of 1-.
In addition, 1- of the invention chloro- 2, in the manufacturing method of 3,3- trifluoro propenes, it is chloro- that the preferably described composition contains 3-
1,1,2,2- tetrafluoropropane, the solid absorbent contain selected from at least one kind of of active carbon, aluminium oxide, zeolite 4A and zeolite 5A,
To remove the chloro- 1,1,2,2- tetrafluoropropane of 3- from the composition.
1- of the invention chloro- 2, the feature of the manufacturing method of 3,3- trifluoro propenes be further include making 3- chloro- 1,1,2,2- tetra-
Dehydrofluorination occurs for fluoro-propane to manufacture containing the chloro- 2,3,3- trifluoro propene of 1- and selected from water, the fluoro- 1- of the chloro- 3,3- bis- of 1-
The process of the composition of at least one kind of compound of propine, oxide and the chloro- 1,1,2,2- tetrafluoropropane of 3-.
Invention effect
Manufacturing method through the invention, can be efficiently from containing 1233yd and selected from water, the fluoro- 1- of chloro- 3, the 3- bis- of 1-
The composition of a kind or more of compound of propine, oxide and HCFC-244ca, which removes, is selected from water, the fluoro- 1- third of the chloro- 3,3- bis- of 1-
1 kind or more of compound of alkynes, oxide and HCFC-244ca.
In addition, manufacturing method through the invention, can efficiently manufacture the 1233yd of high-purity.
Specific embodiment
In the following, embodiments of the present invention will be described.
The 1st embodiment > of <
The manufacturing method of 1233yd as the 1st embodiment of the invention is to make containing 1233yd and chloro- selected from water, 1-
The composition of a kind or more of compound of the fluoro- 1- propine of 3,3- bis-, oxide and HCFC-244ca contacted with solid absorbent with
Remove a kind or more of the compound selected from above-mentioned water, the fluoro- 1- propine of the chloro- 3,3- bis- of 1-, oxide and HCFC-244ca
The manufacturing method of 1233yd.Hereinafter, " selected from water, the fluoro- 1- propine of chloro- 3, the 3- bis- of 1-, a kind of oxide and HCFC-244ca with
On compound " be also denoted as " impurity (A) ", the composition containing 1233yd and impurity (A) is also denoted as " purifying with composition ".It is logical
Crossing contacts purifying with composition with solid absorbent, removes impurity (A) from purifying composition, 1233yd is purified, can
Manufacture the 1233yd of high-purity.Herein, the removing about impurity (A) can remove part of it, can also all remove.
[purifying composition]
The purifying of present embodiment is the composition containing 1233yd and impurity (A) with composition, is not limited especially
It is fixed.In addition, purifying composition contains the other compositions in addition to 1233yd and impurity (A).Other compositions are 1233yd
Manufacturing process in the by-product etc. that generates.Purifying can be liquid with composition, be also possible to gas.
As the purifying composition of present embodiment, such as it is able to use for the purpose of manufacturing 1233yd and makes various raw materials
The reaction product containing 1233yd of ingredient reaction and acquisition.That is, as described later, in the manufacturing process of 1233yd, anti-
In the case where answering product to include 1233yd and impurity (A), the reaction product directly can be used as purifying composition.Separately
Outside, water cleaning can be carried out to reaction product or alkali cleans, will eliminate hydrogen fluoride contained by reaction product, hydrogen chloride etc.
Composition after acidic materials is used as purifying composition.
In the manufacturing method of present embodiment, as the purifying composition contacted with solid absorbent, can specifically it enumerate
The resulting reaction product containing 1233yd of the method for (I) or (II) below.
(I) make under stream of nitrogen gas using chromium oxide as catalyst HCFC-244ca in the gas phase with the method for hydrogen fluoride reaction
(II) keep HCFC-244ca de- in 40~80 DEG C of at a temperature of generation using potassium hydroxide or sodium hydroxide as reactant
The method of hydrogen fluoride reaction
(1233yd)
1233yd is the fluoroolefin between carbon atom-carbon atom with double bond, therefore the service life in an atmosphere is short, smelly
Oxygen consumption latent energy value and chamber effect potential value are low.
There is the Z formula body and E formula body as geometric isomer according to the position of the substituent group in double bond in 1233yd.This theory
In bright book, without illustrate used the abbreviation of chemical combination name or compound in the case where, indicate Z formula body, E formula body and
Any one of the mixture of Z formula body and E formula body, the case where (E) or (Z) are marked with after the abbreviation of chemical combination name or compound
Under, indicate the E formula body or Z formula body of each compound.For example, 1233yd (Z) indicates that Z formula body, 1233yd (E) indicate E formula body.
The boiling point of 1233yd (Z) is about 54 DEG C, and the boiling point of 1233yd (E) is about 48 DEG C, is the excellent chemical combination of drying property
Object.In addition, even if boiling and form steam, which is also the temperature near respective boiling point, thus for be easy by
Resin component etc. to the influence of heat does not also easily cause adverse effect.In addition, 1233yd is with no ignition point, surface tension and glues
Spend it is low, be also easy the excellent performances as cleaning solvent and coating solvent such as evaporation at normal temperature.
The purifying composition of present embodiment contains micro 1233yd, but the content of 1233yd is relative to purifying
With the total amount of composition preferably more than 5 mass %, more preferably more than 10 mass %, further preferably 50 mass % with
On, particularly preferably more than 70 mass %, most preferably more than 80 mass %.If the content of 1233yd the lower limit value with
On, then the removal efficiency of impurity (A) is good.The content of 1233yd and impurity (A) in the purifying composition of present embodiment
It is not particularly limited, from the point of view of the removal efficiency of impurity (A), mole represented by preferably (impurity (A))/(1233yd)
Than being lower than 1, more preferably 0.001~0.7, further preferably 0.1~0.2.
(water)
The purifying of present embodiment in composition sometimes with the water generated in the manufacturing process of such as 1233yd, or
The manufacturing process of 1233yd resulting reaction product mixed water when being cleaned by water or alkali.Purifying composition contains the feelings of water
Under condition, from the point of view of the removal efficiency of impurity (A), purifying is with the content of the water in composition relative to purifying composition
Total amount preferably in 1 mass % hereinafter, more preferably in 0.5 mass % hereinafter, further preferably below 0.1 mass %.
(the fluoro- 1- propine of the chloro- 3,3- bis- of 1-)
Purifying is used in composition sometimes with the chloro- 3,3- bis- of 1- generated in the manufacturing process of 1233yd as by-product
Fluoro- 1- propine.The 1- fluoro- 1- propine of chloro- 3,3- bis- is given birth to by carrying out the dehydrofluorination of 1233yd shown in following formula [1]
At.
CHCl=CFCHF2→CCl≡CCHF2+HF…[1]
In the case that purifying composition contains the fluoro- 1- propine of chloro- 3, the 3- bis- of 1-, from the angle of the removal efficiency of impurity (A)
Degree considers that the content of the fluoro- 1- propine of chloro- 3, the 3- bis- of 1- in purifying composition is preferred relative to the total amount of purifying composition
In 1 mass % hereinafter, more preferably in 0.5 mass % hereinafter, further preferably below 0.1 mass %.
(oxide)
Sometimes with oxide in the purifying composition of present embodiment.
Oxide (oxide) be 1233yd reacted with oxygen and the oxide that generates.Specifically, the chloro- 2- (two of 3- can be enumerated
Methyl fluoride) -2- fluoro ethylene oxide (chemical formula (A)), bis- fluoracyl fluoride of 2,2- (chemical formula (B)), formyl chloride (chemical formula
(C)), the fluoro- 1- peroxidating base -1- propylene (chemical formula (D)) of the chloro- 2,3,3- tri- of (E, Z) -1-, the fluoro- 3- mistake of the chloro- 1,1,2- tri- of 3-
Aoxidize base -1- propylene (chemical formula (E)), the fluoro- 3- peroxidating base -1- propylene (chemical formula (F)) of the chloro- 2,3,3- tri- of (E, Z) -1-
Deng.
[changing 1]
[changing 2]
[changing 3]
[changing 4]
[changing 5]
[changing 6]
Gas-chromatography 2- chloro- to 3- (difluoromethyl) -2- fluoro ethylene oxide, bis- fluoracyl fluoride of 2,2-, first can be utilized
Acyl chlorides is analyzed to quantify.The fluoro- 1- peroxidating base -1- propylene of the chloro- 2,3,3- tri- of (E, Z) -1-, the fluoro- 3- of the chloro- 1,1,2- tri- of 3-
With-O-O-H structure as the fluoro- 3- peroxidating base -1- propylene of the chloro- 2,3,3- tri- of peroxidating base -1- propylene, (E, Z) -1-
Hydroperoxides quantitatively by sodium iodide shown in following reaction equations [2], [3] titration and sodium thiosulfate back titration come into
Row.ROOH indicates arbitrary hydroperoxides.
ROOH+2NaI+H2O→I2+2NaOH+ROH…[2]
I2+2Na2S2O3→Na2S4O6+2NaI…[3]
Above-mentioned titration and back titration progress specific as follows.In the sample solution containing hydroperoxides (ROOH) of about 50mL
The acetone soln of the middle sodium iodide (NaI) for mixing 2.5 mass %, about 40mL, further the cold water of additional mixing about 50mL, passes through
Iodine (the I generated as shown in the reaction equation [2]2) mixed liquor coloured into yellowly.It will there is a situation where colour at this time
It is determined as the Monitoring lower-cut of hydroperoxides or less.In the case where there is coloring, with the thiosulfuric acid of 0.01mol/L (0.01N)
Sodium (Na2S2O3) aqueous solution is to mixed liquor progress back titration, up to decoloration.The quantitative values of hydroperoxides use the drop
Fixed experiment value is found out by following calculating formulas.
Hydroperoxides [quality ppm]
={ Na2S2O3Aqueous solution consumption [mL] × Na2S2O3Molar concentration [mol/mL] × (1/2) × ROOH molecule
Amount }/sample solution weight [g] × 106
In the case that purifying composition contains oxide, from the point of view of the removal efficiency of impurity (A), group is used in purifying
Close object in oxide content relative to purifying composition total amount preferably in 0.1 mass % hereinafter, more preferably 0.05
Quality % is hereinafter, further preferably below 0.01 mass %.
(HCFC-244ca)
HCFC-244ca is used for example as the manufacture raw material of 1233yd.At this point, HCFC-244ca includes as unreacting material
In purifying composition.In the case that purifying composition contains HCFC-244ca, from the angle of the removal efficiency of impurity (A)
Consider, the content of the HCFC-244ca in purifying composition preferably in 1 mass % hereinafter, more preferably in 0.5 mass % hereinafter,
Further preferably below 0.1 mass %.
[solid absorbent]
The solid absorbent absorption of present embodiment is selected from water, the fluoro- 1- propine of the chloro- 3,3- bis- of 1-, oxide and HCFC-
1 kind or more of the compound of 244ca.As solid absorbent, active carbon, zeolite, silica, aluminium oxide etc. can be enumerated.Gu
Body adsorbent can be used alone a kind, can also be applied in combination with two or more.
Solid absorbent is preferably the dry gas for first passing through 100 DEG C~400 DEG C in advance before contacting with purifying with composition
The adsorbent heated, or the catalyst heated under reduced pressure.It can be improved impurity (A) whereby
Absorption property.
(active carbon)
By-product when active carbon used in present embodiment can enumerate such as timber, wood powder, coconut husk, pulp manufacture,
バ カ ス, syrup, peat, lignite (Japanese: Ami charcoal), lignite (Japanese: brown charcoal), bituminous coal, anthracite, petroleum distillation residue at
Point, department of botanys' raw material or the fossil system raw material such as asphalt, coke, coal tar, phenolic resin, vinyl chloride resin, vinyl acetate
Ester resin, melamine resin, urea resin, resorcinol resin, celluloid, epoxy resin, polyurethane resin, polyester tree
The synthetic rubber such as the various synthetic resin such as rouge, acrylic resin, polyamide, polybutene, polybutadiene, polychlorobutadiene,
Active carbon obtained from other synthetic woods, the charing for synthesizing slurrying isoreactivity carbon feedstock, activation.In these activated carbon raw materials,
Coconut husk to impurity (A) have high absorption property, therefore it is preferable to use.
As active carbon used in present embodiment, from the point of view of the good adsorption performance of impurity (A), -196
(ASAP2405 etc. of Mike Mo Ruitike company (Micromeritics) system) is determined by nitrogen adsorption method at DEG C.Make
For pore characteristics, specific surface area is preferably 600m2/ g~2500m2/ g, more preferably 1000m2/ g~1600m2/ g, average pore
Diameter is preferably 1.6nm~3.5nm, more preferably 1.7nm~2.0nm.Pore volume is preferably 0.25mL/g~1.5mL/g,
More preferably 0.3mL/g~1.0mL/g.
In addition, similarly, from the point of view of the good adsorption performance of impurity (A), as work used in present embodiment
Property charcoal by the general physics value of JIS K1474 test method determination, dry loss of weight is in 5.0 mass fraction % hereinafter, preferably greater than 0
Quality % and in 5.0 mass % hereinafter, burning remaining residual component preferably below 5.0 mass fraction %.Packed density is preferably
0.25g/mL~0.85g/mL, more preferably 0.35g/mL~0.60g/mL.PH is preferably 4.0~12.0, more preferably 5.0~
11.0.Acetone absorption property is preferably the 14.0 mass fraction % of mass fraction %~41.0, more preferably 25.0 mass fraction %
~39.0 mass fraction %.Iodine absorption property is preferably 600mg/g~2600mg/g, more preferably 900mg/g~1600mg/g.
Hardness is preferably 90.0 mass fraction of mass fraction %~100.0 %.
As the shape of active carbon used in present embodiment, forming charcoal, 4 mesh of length 2mm~10mm or so can be enumerated
The crushing charcoals of~50 mesh or so, granulated carbon etc., from the point of view of activity, preferably 4 mesh~50 mesh crushing charcoal or length 2mm
The forming charcoal of~5mm.Wherein, from the point of view of economically advantageous, the preferred active carbon of comminution, particularly preferred comminution
Cocoanut active charcoal.Commercially available product can be used in active carbon, and the active carbon manufactured by well known method in addition can also be used.Further,
As active carbon, it can be used and implement the pretreated active carbons such as sour processing, heat treatment, steam treatment.
(zeolite)
Zeolite used in present embodiment is the synthetic zeolite with chemical composition shown in following below formula [4] or [5].
KxNay[(AlO2)12(SiO2)12]·27H2O…………[4]
(wherein, x+y=12, x:y=4:6~8:2.)
KxNay[(AlO2)86(SiO2)106]·276H2O…………[5]
(wherein, x+y=86, x:y=4:6~8:2.)
As zeolite used in present embodiment, such as zeolite 3A, 4A and 5A can be enumerated.Zeolite 3A, 4A and 5A are that have
The synthetic zeolite of the fine pore of 0.25nm~0.45nm.
The zeolite 3A of present embodiment refers to the synthetic zeolite of the fine pore with 0.28nm ± 0.03nm.Wherein, due to
Flexible and movement energy, the synthetic zeolite 3A for entering the molecule in emptying aperture under common operation temperature can be such that effective diameter reaches
The molecule of 0.3nm passes through.
The zeolite 4A of present embodiment refers to the synthetic zeolite of the fine pore with 0.35nm ± 0.03nm.
The zeolite 5A of present embodiment refers to the synthetic zeolite of the fine pore with 0.42nm ± 0.03nm.
As this zeolite, the zeolite marked with 3A, 4A and 5A can be enumerated in A type synthetic zeolite.As commercially available product, have point
Son sieve (Japanese: モ レ キ ュ ラ ー シ ー Block) 3A, 4A, 5A (commodity of UNION Showa Corporation (ユ ニ オ Application Showa society)
Name) etc..In addition, the commercially available product as X-type synthetic zeolite, there is molecular sieve 13X.In addition, other than zeolite 3A, 4A or 5A,
The molecular sieve that can be used in combination 13X.In addition, the fine pore of solid absorbent can be measured by constant volume formula gas adsorption method.Make
For adsorbed gas used in above-mentioned constant volume formula gas adsorption method, N can be enumerated2、CO2、CH4、H2, Ar etc..
(silica)
In present embodiment, silica is that mainly have SiO2Chemical composition compound.It, can as silica
Enumerate Porous synthetic silica gel, mesoporous silicon oxide, silica alumina etc..Silica can be used alone 1
Kind, it can also be applied in combination with two or more.
As the shape for the silica for being used as solid absorbent, powdered, finely particulate, graininess, film can be enumerated
Shape etc..The shape of silica can suitably select suitable shape according to reaction method.From the angle of the absorption property of impurity (A)
Consider, being preferably shaped to for silica is powdered or microgranular.Wherein, purifying group of the microgranular silica in liquid
State that is evenly dispersed in object and being in dispersion liquid is closed, therefore easy to operate.In addition, microgranular silica is easy in reactor
It is interior to form aftermentioned adsorption layer.
Porous synthetic silica gel used in present embodiment is the punctulate silica dioxide gel of tool.It is porous
The shape of matter synthetic silica gel can be the non-spherical of crushing, be also possible to spherical, recycling high from intensity, easy
From the point of view of, it is preferably spherical.In addition, " spherical " is not limited to ball, it further include the spherical shape that elliptical shape ball etc. slightly deforms." ball
Shape " preferably average spherical degree is 0.5 or more, more preferably 0.85 or more.
In addition, the average grain diameter of spherical Porous synthetic silica gel is preferably 0.1 μm~10000 μm, it is more excellent
It is selected as 1 μm~5000 μm.The average fine pore of spherical Porous synthetic silica gel is preferably 0.5nm~100nm, more
Preferably 2nm~50nm.The specific surface area of spherical Porous synthetic silica gel is preferably 10m2/ g~10000m2/ g,
More preferably 30m2/ g~1000m2/g.Except these ranges, the amount of effective particle and pore may cause
It reduces, reaction speed reduces, side reaction carries out etc..
Porous synthetic silica gel is easy to obtain as commercially available product, can be synthesized by well known method.Into one
Step, also implementable activation etc. pre-processes the Porous synthetic silica gel.For example, synthesizing dioxy as Porous
The commercially available product of SiClx gel can enumerate silica dioxide gel (シ リ カ ゲ Le) 40, silica for being commonly used for chromatographic carrier
Gel 60, Wako Pure Chemical Industries, Ltd. (Wako Pure Chemical Industries, Ltd.) system Wakosil C-200, Wakosil C-300 and
The chemical society in Kanto Kagaku K. K. (Seki east) system spherical silicon dioxide etc..
In addition, average grain diameter is the weight basis that sieve method specified in JIS Z 8801 is measured in this specification
The value of 50% average grain diameter.Specific surface area is able to use N2、CO2、CH4、H2, Ar etc. passes through gas adsorption method and measures.
Mesoporous silicon oxide refers to uniform and regular mesoporous (pore of diameter 2nm~50nm) and mainly has
SiO2Chemical composition inorganic matter.The shape of mesoporous silicon oxide can enumerate spherical, powdered, microgranular, film-form etc..Its
In, from large specific surface area, intensity is high, is easy recycling uses, can be more preferably spherical easily from the point of view of industrial production
Particle.The fine pore of mesoporous silicon oxide is preferably 2nm~50nm, more preferably 2nm~10nm.The pore of mesoporous silicon oxide
Diameter is if it is less than 2nm, then diffusion velocity of the purifying composition into mesoporous silicon oxide is low, there are absorption property reduce can
It can property.On the other hand, the fine pore of mesoporous silicon oxide is if it is greater than 50nm, then purifying composition and mesoporous silicon oxide without
Method comes into full contact with, and may be unable to get high selectivity and high yield.
The BET specific surface area of mesoporous silicon oxide is preferably 10m2/ g~3000m2/ g, more preferably 50m2/ g~
3000m2/g.The mesoporous silicon oxide of this BET specific surface area can be easily manufactured, and can efficiently with purifying group
Object contact is closed with effective adsorbing contaminant (A).
In addition, the average grain diameter of mesoporous silicon oxide is preferably 0.2 μm~10000 μm, more preferably 1 μm~5000 μm.
As the typical example of mesoporous silicon oxide, MCM-41, MCM-48, MCM-50, SBA-1, SBA-11, SBA- can be enumerated
15, SBA-16, FSM-16, KIT-5, KIT-6, HMS (hexagonal crystal), MSU-F, MSU-H etc..These mesoporous silicon oxides can be with city
Seller's formula is obtained and is used.In addition, can be synthesized by known method.
Silica alumina is with silica (SiO2) and aluminium oxide (Al2O3) be principal component composite oxides, can
To be crystallized oxide, it is also possible to noncrystalline oxide.It is preferred that silica and aluminium oxide in silica alumina
Amount is aggregated in 95 mass % or more, and the containing ratio of silica is in 50mol% or more.
As the shape of silica alumina, spherical, powdered, microgranular, film-form etc. can be enumerated.Wherein, from than
Surface area is big, intensity is high, is easy recycling uses, can be easily from the point of view of industrial production, preferably spherical particle.
The average grain diameter of spheroidal particle silica alumina is preferably 0.2 μm~20000 μm, more preferably 1 μm~
10000μm.The average fine pore of the silica alumina of spheroidal particle is preferably 1nm~100nm, and more preferably 2nm~
50nm.The specific surface area of the silica alumina of spheroidal particle is preferably 10m2/ g~10000m2/ g, more preferably 30m2/g
~1000m2/g.The silica alumina of the spheroidal particle of above-mentioned average grain diameter and specific surface area can be easily manufactured.Separately
Outside, if it is above-mentioned average grain diameter or specific surface area, then, the absorption property of impurity (A) high with the diffusion velocity of composition is purified
It is excellent.
Silica alumina is easy to obtain as commercially available product, and can be synthesized by well known method.Further, should
Silica alumina can also the pretreatment such as implement activation as needed.
As the commercially available product of silica alumina, such as Fuji SILYSIA Chemical Co., Ltd. (Fuji シ リ can be enumerated
シ ア chemistry society) system silica alumina 308, wave catalyst day and be melted into Co., Ltd.'s (wave day catalyst chemical conversion society) system
N633HN, N631HN, N633L, N631L, the Al-MCM- of the Ritchie Sigma Ao get company (シ グ マ ア Le De リ ッ チ society) system
41, Al-MSU-F etc..
(aluminium oxide)
Aluminium oxide is that mainly have Al2O3Chemical composition compound.As aluminium oxide, preferably activated alumina.Activity
Aluminium oxide is inorganic porous body, is the quasi-steady from aluminium hydroxide into the transition process of the Alpha-alumina as high-temperature stable phase
The aluminium oxide of phase.Large specific surface area then good adsorption performance, therefore activated alumina is preferably from noncrystalline to gama-alumina
Aluminium oxide in range.
The forming such as spherical, cylindric, the long square column of being preferably shaped to for activated alumina, sheet, hollow cylindrical, honeycomb
Body, the shot-like particle of partial size 3mm~8mm is in terms of the pressure loss easy to operate and when can be reduced as far as solid-vapor contact
Consideration is preferred.
The pore for including in activated alumina be divided into micropore (20 angstroms of fine pore or less), macropore (500 angstroms of fine pore with
On) and it is mesoporous between the two.Think in these pores, micropore carries out physical absorption to impurity (A), mesoporous and big
Mitigate the diffusion law speed of purifying composition in hole.Pore volume shared by micropore is preferably the 10%~50% of total pore volume
In range.The kind of raw material when the fine pore and volume of mesoporous and macropore in activated alumina can be manufactured according to activated alumina
The adjusting of class and molding condition is adjusted.
From the point of view of the good adsorption performance of impurity (A), the BET specific surface area of activated alumina is preferably 50m2/g
~350m2/ g, more preferably 100m2/ g~350m2/g.In addition, the average fine pore by determination of nitrogen adsorption of activated alumina
Preferably 5 angstroms~200 angstroms, more preferably 10 angstroms~150 angstroms.In addition, the pore volume of activated alumina be preferably 0.1mL/g~
0.8mL/g, more preferably 0.2mL/g~0.5mL/g.
(contact method of solid absorbent and purifying composition)
In the manufacturing method of present embodiment, make the purifying composition containing 1233yd and impurity (A) and above-mentioned solid
Adsorbent contact, purifying is adsorbed to solid absorbent with the impurity (A) in composition and removes whereby.
Purifying composition when contacting with solid absorbent can be gas (gaseous state), can also be liquid (liquid).This reality
Apply in the manufacturing method of mode, in the case where solid absorbent of more than two kinds is applied in combination, the solid absorbent that is contacted it is suitable
Sequence is not particularly limited.For example, purifying can be contacted successively with solid absorbent of more than two kinds with composition, it can also be by two or more
Solid absorbent mixing after contact simultaneously.In the case where successively contacting, used solid absorbent passes through aftermentioned respectively
Contact method is contacted with purifying with composition and solid adsorption material.
Hereinafter, to use gaseous state purifying to be illustrated for the method for composition.In this method, such as into reactor
Filled solid adsorbent is to form adsorption layer, and circulate the gaseous purifying composition containing 1233yd in the adsorption layer, by
This can be such that solid absorbent is contacted with purifying with composition.Solid absorbent and purifying composition based on this method connect
Touching can be batch-type, be also possible to continous way.
The packed density of solid absorbent in adsorption layer is preferably in 0.1g/cm3More than, more preferably in 0.25g/cm3With
On.If the packed density of solid absorbent is larger than lower limiting value, the loading of the solid absorbent of per unit volume is more, energy
Enough increase the treating capacity of gaseous purifying composition, so that the removal efficiency of the impurity (A) other than 1233yd is improved.It inhales
Attached layer can be 1 layer, be also possible to 2 layers or more.For adsorption layer in the case where 2 layers or more, these adsorption layers can be also straight side by side
Column.
For purifying is maintained gaseous state with composition, the temperature of adsorption layer when contact is preferably the boiling point of 1233yd
Above 60 DEG C~100 DEG C, more preferably 70 DEG C~90 DEG C.If the temperature of adsorption layer is larger than lower limiting value, solid absorption
Agent is improved the removal efficiency of impurity (A).If the temperature of adsorption layer is below the upper limit, composition after purification
Cooling required energy is less, and equipment etc. is also simple.
Pressure (gauge pressure, same below) preferably 10kPa~500kPa, more preferable 90kPa when contact in reactor
~300kPa.If pressure is larger than lower limiting value, the removal efficiency of impurity (A) is improved.If pressure upper limit value with
Under, then operability is good, and equipment etc. can be realized simply.
The time of contact of the gaseous purifying composition and adsorption layer that circulate in adsorption layer is preferably 1 second~1000 seconds,
More preferably 3 seconds~300 seconds.If the time of contact of gaseous purifying composition and adsorption layer is larger than lower limiting value, miscellaneous
The removal efficiency of matter (A) is improved.If the time of contact of gaseous purifying composition and adsorption layer is below the upper limit,
It then can be completed in the purifying of purifying composition using small adsorption layer, equipment etc. is also simple.In addition, circulating in adsorption layer
In the method for purifying composition containing 1233yd, when time of contact is equivalent to delay of the purifying composition in reactor
Between, it can be controlled with composition to the supply amount (flow) of reactor by adjusting purifying.It is used using the purifying of aftermentioned liquid
The case where composition, is similarly such.
In addition, from the point of view of removal efficiency, impurity contained by the gaseous purifying composition that circulates in adsorption layer
(A) total amount relative to 1 mass parts of solid absorbent in adsorption layer preferably 0.05 below the mass, more preferably in 0.02 matter
Measure part or less.That is, preferably adjusting gaseous state contact with solid absorbent in method using gaseous state purifying composition and purifying use
The amount of composition so that impurity (A) relative to solid absorbent ratio in above-mentioned upper limit value hereinafter, then being contacted.
As purifying composition gas and reactor used in the contact of solid absorbent, as long as can fill solid
Body adsorbent is to form the reactor of adsorption layer.As the material of reactor, such as glass, iron, nickel or with this can be enumerated
A little ingredients are the fluororesin etc. of alloy, tetrafluoroethylene-perfluoro (alkyl vinyl ether) copolymer (PFA) of principal component etc..
Then, the method for using purified liquid composition is illustrated.This method with using gaseous state purifying with combining
The method of object is same, can use and form adsorption layer in reactor, the purifying composition of the liquid containing 1233yd is made to exist
The method to circulate in the adsorption layer.In addition, can be used in the reactor for containing solid absorbent, solid absorbent is impregnated
In purifying composition, the method that is mixed, stirred as needed.Solid absorbent and purifying based on these methods are used
The contact of composition can be batch-type, be also possible to continous way.
When purifying is contacted with composition with liquid condition and solid absorbent, purifying can be adjusted under normal pressure with composition
Boiling point temperature below is to form liquid.In addition, purifying composition can be dissolved in a solvent to form liquid.As at this time
The solvent used can be with the methods of distillation easily from group after purification by using the solvent different from 1233yd boiling point
It closes object and removes the solvent.
Temperature when solid absorbent and purifying are contacted with composition in reactor is preferably -30 DEG C~70 DEG C, more preferably
It is 10 DEG C~40 DEG C.If the temperature in reactor is larger than lower limiting value, the removal rate of the impurity other than 1233yd is obtained
It improves.If the temperature in reactor is below the upper limit, the energy that the cooling of composition after purification is required is less, equipment
Deng also simple.
Pressure when solid absorbent and purifying are contacted with composition in reactor is preferably 0kPa~200kPa, more preferably
For 100kPa~150kPa.If pressure is larger than lower limiting value, the removal rate of the impurity other than 1233yd is improved.Pressure
If power is below the upper limit, operability is good, and equipment etc. can be realized simply.
In the method for the purifying composition containing 1233yd that circulates in adsorption layer, the liquid that circulates in adsorption layer it is pure
The time of contact of change composition and adsorption layer is preferably 1 second~1000 seconds, more preferably 3 seconds~300 seconds.The purifying of liquid is used
If the time of contact of composition and adsorption layer is larger than lower limiting value, the removal efficiency of impurity (A) is improved.Liquid it is pure
If changed with the time of contact of composition and adsorption layer below the upper limit, it is using small adsorption layer in the purifying of composition
Achievable, equipment etc. is also simple.
The preferred embodiment of the composition of the packed density and adsorption layer of the solid absorbent of adsorption layer is used with using gaseous state purifying
The method of composition is identical.
Solid absorbent is impregnated in the method for purifying composition in the reactor for accommodating solid absorbent, instead
Answering the time of contact of purified liquid composition and solid absorbent in device is preferably 1 hour~100 hours, and more preferably 3 is small
When~60 hours.If the purifying composition of liquid and the time of contact of solid absorbent are larger than lower limiting value, impurity (A)
Removal efficiency be improved.If the purifying of liquid uses the time of contact of composition and solid absorbent below the upper limit,
It then can be completed in the purifying of purifying composition using a small amount of solid absorbent, equipment etc. is also simple.
Solid absorbent is impregnated in the method for purifying composition in reactor, in the purifying of purifying composition
Afterwards, composition after purification can be separated with solid absorbent by settling or filtering.
In addition, the purifying of the liquid contacted with solid absorbent is used from the point of view of the removal efficiency for improving impurity (A)
The total amount of impurity contained by composition (A) relative to 1 mass parts of solid absorbent preferably 0.05 below the mass, more preferably exist
0.02 below the mass.That is, preferably adjusting the purifying contacted with solid absorbent in method using purified liquid composition
With the liquid measure of composition so that above-mentioned impurity (A) relative to solid absorbent ratio in above-mentioned upper limit value hereinafter, then carrying out
Contact.
As purified liquid composition and reactor used in the contact of solid absorbent, as long as can for example hold
Receive solid absorbent reactor or be capable of forming the reactor of the adsorption layer being made of solid absorbent.As reactor
Material, such as glass, iron, nickel or using these ingredients as the alloy of principal component, tetrafluoroethylene-perfluoro (alkyl vinyl can be enumerated
Base ether) copolymer (PFA) etc. fluororesin etc..It, can example as the reactor that mixed liquor is mixed and contacted with solid absorbent
The reactor that purifying composition can be made to contact with liquid condition with solid absorbent with required temperature, pressure is lifted, such as
Autoclave etc. can be enumerated.
(composition after purification)
In general, according to type (material composition and the pore of the composition of the composition as purifying object and solid absorbent
Size), the compound that solid absorbent is easy absorption is different.Containing 1233yd and selected from water, the fluoro- 1- of the chloro- 3,3- bis- of 1-
The composition of a kind or more of compound of propine, oxide and HCFC-244ca be purify object present embodiment in, such as
Water is easily adsorbed at zeolite, is preferably adsorbed in zeolite 3A or zeolite 4A.In addition, water is also easily adsorbed at aluminium oxide and titanium dioxide
Silicon.Therefore, in the purifying of present embodiment, use aluminium oxide, silica or zeolite (especially zeolite 3A or 4A) as admittedly
Body adsorbent is contacted with the purifying containing 1233yd and water with composition, and the water in composition can be selectively removed whereby,
1233yd is purified.
Purifying is easy to be adsorbed to active carbon, aluminium oxide with the oxide in composition.Therefore, the purifying of present embodiment
In, use active carbon or aluminium oxide as solid absorbent, is contacted with the purifying containing 1233yd and oxide with composition, by
Oxide can be selectively removed to manufacture 1233yd in this.
In addition, 1- chloro- 3,3- bis- fluoro- 1- propine of the purifying in composition be easily adsorbed at active carbon, silica and
Aluminium oxide.Therefore, use active carbon, silica or aluminium oxide as solid absorbent, and contain 1233yd and 1- chloro- 3,3-
The purifying of two fluoro- 1- propine is contacted with composition, and it is fluoro- efficiently to remove chloro- 3, the 3- bis- of 1- with composition from purifying whereby
1- propine is to manufacture 1233yd.
In addition, purifying is easily adsorbed at active carbon, aluminium oxide and zeolite 4A, 5A with the HCFC-244ca in composition.Cause
This, uses active carbon, zeolite 4A or zeolite 5A as solid absorbent, with the purifying group containing 1233yd and HCFC-244ca
Object contact is closed, can efficiently remove HCFC-244ca from purifying with composition whereby to manufacture 1233yd.
It, can will be pure as such, by the way that a kind of solid absorbent is used alone or is applied in combination solid absorbent of more than two kinds
Change the impurity (A) contained by composition to remove with the required desired degree of compound.
Impurity contained by purifying composition (A) is removed by the manufacturing method of present embodiment, can be obtained whereby
The composition that impurity (A) content reduces.
In addition, the content of the 1233yd in the composition of the manufacturing method through present embodiment after purification is preferably in 90 matter
% or more is measured, more preferably more than 95 mass %, further preferably more than 99 mass %.The water in composition after purification contains
Amount is preferably in 0.005 mass % hereinafter, the content of the fluoro- 1- propine of chloro- 3, the 3- bis- of 1- is preferably in 0.001 mass % hereinafter, more excellent
0.0005 mass % is selected in hereinafter, further preferably below 0.0003 mass %.In addition, HCFC- in composition after purification
The content of 244ca is preferably in 0.1 mass % hereinafter, more preferably below 0.058 mass %.If each ingredient is in the upper limit value
Hereinafter, can then play various performances in a variety of applications where.The content of oxide is preferably in 5 mass in composition after purification
Ppm or less.The content of oxide if in the upper limit value hereinafter, if can be substantially prevented from solvent compositions stability drop
It is low.In addition, the content of oxide if in the upper limit value hereinafter, if can not also be reduced to the limit of 0 mass ppm.After purification
Composition in oxide content preferably more than 1 mass ppm, more preferably more than 2 mass ppm.If in the lower limit
More than value, then the oxidation of 1233yd is inhibited, the excellent in stability of solvent compositions.
The 2nd embodiment > of <
The manufacturing method of the 1233yd of 2nd embodiment of the invention includes manufacturing the purifying composition containing 1233yd
Process.
It, can be by the resulting reaction of manufacturing process of 1233yd shown in (I) or (II) in the manufacturing method of present embodiment
Product removes blend compositions obtained by acidic materials etc. as purifying composition from reaction product.As such, to pure
Change with composition carry out the first embodiment described above shown in purify, can be efficient from the composition containing 1233yd and impurity (A)
Ground removes impurity (A).
(I) make under stream of nitrogen gas using chromium oxide as catalyst HCFC-244ca in the gas phase with the method for hydrogen fluoride reaction
Make the feedstock composition containing HCFC-244ca and hydrogen fluoride that there is the anti-of the catalyst layer for being filled with chromium oxide
It answers and is reacted under gas phase in device, generate the composition containing 1233yd.
In the gas phase catalytic reaction of this HCFC-244ca and hydrogen fluoride, it can obtain containing 1233yd and hydrogen chloride etc.
The reaction product of acidic materials.Then, acidic materials contained by reaction product are removed by alkali cleaning etc., can be obtained
Blend compositions.As the compound in addition to 1233yd contained in blend compositions, in addition to as unreacting material
Other than HCFC-244ca, the fluoro- 1- propine of chloro- 3, the 3- bis- of water, 1-, HCFC-245ca, 2,3,3- trifluoro propene (H can be also enumerated2C
=CF-CHF2), 1,2,3,3- tetrafluoropropene (HFC=CF-CHF2), the compounds such as oxide.
The reaction product obtained like this or blend compositions are used as purifying composition, carry out above-mentioned 1st embodiment party
It purifies, can efficiently remove the impurity (A) in purifying composition shown in formula.In reaction product or blend compositions
And the other compositions other than 1233yd contained in composition after purification can be removed by method known to distillation etc. to required
Degree.In addition, discharging and recycling from solid absorbent by the HCFC-244ca that solid absorbent is separated from 1233yd, whereby
It can be recycled as a part of raw material.
(II) using potassium hydroxide or sodium hydroxide as reactant make HCFC-244ca 40 DEG C~80 DEG C at a temperature of occur
The method of dehydrofluorination
Issue HCFC-244ca in 40 DEG C~80 DEG C of temperature
Raw dehydrofluorination, generates the composition containing 1233yd.In above-mentioned reaction, for the purpose of promoting reaction, preferably turn in phase
Dehydrofluorination is carried out in the presence of shifting catalyst.In addition, the hydrogen-oxygen in potassium hydroxide aqueous solution or sodium hydrate aqueous solution
The mole that the amount of change potassium or sodium hydroxide is 1~3 times preferably with respect to the molal quantity of HCFC-244ca.
Make at a temperature of generation defluorinate of the HCFC-244ca at 40~80 DEG C using potassium hydroxide or sodium hydroxide as reactant
In the synthetic method of hydrogen reaction, the reaction product containing 1233yd can be obtained.It is removed as what reaction product contained
Compound other than 1233yd can also enumerate the fluoro- 1- of chloro- 3, the 3- bis- of water, 1- in addition to the HCFC-244ca as unreacting material
The compounds such as propine, oxide.
The reaction product obtained like this is used as purifying composition, purified shown in the first embodiment described above,
Efficiently the impurity (A) in purifying composition can be removed.Contained in reaction product and composition after purification
Other compositions other than 1233yd can be removed by method known to distillation etc. to required degree.In addition, passing through solid absorbent
The HCFC-244ca separated from 1233yd is discharged and is recycled from solid absorbent, can be followed whereby as a part of raw material
Ring utilizes.
Embodiment
Hereinafter, however, the present invention is not limited to these examples by the way that examples illustrate the present invention.
(analysis method)
The content (containing ratio) for analyzing the ingredient other than the water and hydroperoxides in object composition object passes through gas phase color
Spectrum is analyzed.Use DB-1301 (long 250 μ m of 60m × internal diameter thick 1 μm, Agilent Technologies' (ア ジ レ Application ト テ Network
ノ ロ ジ ー Co., Ltd.) system) it is used as column.Water content is analyzed by karl Fischer moisture meter, the content of hydroperoxides
It is analyzed by above-mentioned hydroperoxides measuring method.
In addition, using the analysis of above-mentioned gas-chromatography, karl Fischer moisture meter and hydroperoxides measuring method as a result, finding out
Ratio (quality %), the ratio (matter of water of the chloro- 3,3- bis- of the 1- fluoro- 1- propine of total amount relative to analysis object composition object
Measure %), the ratio (quality %) of the ratio (quality ppm) of oxide and HCFC-244ca.
In addition, the content of oxide is the total amount of the analysis result of above-mentioned gas-chromatography and hydroperoxides measuring method.
(Production Example: the manufacture of 1233yd)
Using the HCFC-244ca of 2000g as raw material, 19.9g tetrabutylammonium chloride is added, reaction temperature is remained
50 DEG C, the potassium hydroxide aqueous solution of the 40 mass % of 2792g has been added dropwise with 30 minutes.Continue to react for 52 hours later, it will
Organic phase and water phase two-phase separation, have recycled organic phase.Simple distillation is carried out to recycle fraction to the organic phase of recycling, is obtained whereby
Composition (purifying composition) containing 1233yd, water, the 1- fluoro- 1- propine of chloro- 3,3- bis- and oxide.
(embodiment 1)
The content of the oxide of the resulting purifying composition containing 1233yd of above-mentioned Production Example passes through above-mentioned gas-chromatography
It is quantified with hydroperoxides measuring method, as a result the chloro- 2- of 3- (difluoromethyl) -2- fluoro ethylene oxide is 20 mass ppm, hydrogen
Peroxide is 19 mass ppm, adds up to the oxide containing 39 mass ppm.Therefore, the purifying group to above-mentioned containing oxide
Close active carbon (Serachem Co., Ltd. that addition is 1 mass % relative to the 1233yd of the 1kg in purifying composition in object
(セ ラ ケ system Co., Ltd.) system, coconut husk class crush shaped activated carbon, product name: Fuji charcoal element B-CW), it is small that 48 are stood at room temperature
When.After 48 hours, from 1233yd isolating active charcoal and the content of oxide is measured, as a result the chloro- 2- of 3- (difluoromethyl) -2- fluoro
Ethylene oxide is 0 mass ppm, hydroperoxides are 2.2 mass ppm, adds up to 2.2 mass ppm.
(embodiment 2)
Into the purifying composition of the above-mentioned oxide containing 39 mass ppm, addition is relative in purifying composition
Activated alumina (Fuji Company Ltd. (Fuji Company Ltd.) system, activated alumina, the product that the 1233yd of 1kg is 1 mass %
Name PSG-D25), stand 48 hours at room temperature.After 48 hours, from 1233yd isolating active aluminium oxide and containing for oxide is measured
Amount, as a result the chloro- 2- of 3- (difluoromethyl) -2- fluoro ethylene oxide is 0 mass ppm, hydroperoxides are 3.2 mass ppm, is added up to
For 3.2 mass ppm.
By embodiment 1,2 it is found that by the way that the composition of the purifying containing 1233yd and active carbon or activated alumina are connect
Touching effectively can remove oxide from purifying composition.
(embodiment 3)
Composition other than oxide in the resulting purified composition containing 1233yd of above-mentioned Production Example is analyzed, is tied
Fruit shown in table 1 to form containing 1233yd, water, the 1- fluoro- 1- propine of chloro- 3,3- bis- and HCFC-244ca.It will be formed shown in table 1
The polypropylene container with cover of 1L is added in the 1233yd of ratio, and into purifying composition, addition is relative in purifying composition
(Serachem Co. Ltd. system, coconut husk class crush shaped activated carbon to the active carbon that the 1233yd of 1kg is 1 mass %, product name: rich
Scholar's charcoal element B-CW), stand 48 hours at room temperature.After 48 hours, from purifying composition isolating active charcoal and oxide is analyzed
Composition in addition, result are to form shown in table 1.
(embodiment 4)
In addition to using activated alumina (Fuji Company Ltd.'s system, activated alumina, product name PSG-D25) to substitute active carbon
In addition, it is handled by method similarly to Example 3.After processing, from purifying composition isolating active aluminium oxide and divide
The composition other than oxide is analysed, result is to form shown in table 1.
(embodiment 5)
In addition to using zeolite 3A (UNION Showa Corporation system, trade name: molecular sieve 3a) to substitute other than active carbon, lead to
The method crossed similarly to Example 3 is handled.After processing, zeolite 3A is separated from purifying composition and is analyzed other than oxide
Composition, result be table 1 shown in form.
(embodiment 6)
In addition to using zeolite 4A (UNION Showa Corporation system, trade name: molecular sieve 4A) to substitute other than active carbon, lead to
The method crossed similarly to Example 3 is handled.After processing, zeolite 4A is separated from purifying composition and is analyzed other than oxide
Composition, result be table 2 shown in form.
(embodiment 7)
In addition to using zeolite 5A (UNION Showa Corporation system, trade name: molecular sieve 5A) to substitute other than active carbon, lead to
The method crossed similarly to Example 3 is handled.After processing, zeolite 5A is separated from purifying composition and is analyzed other than oxide
Composition, result be table 2 shown in form.
(embodiment 8)
In addition to using silica dioxide gel (Kanto Kagaku K. K.'s system, product name: spherical silicon dioxide gel (partial size
63-210 μm)) it substitutes other than active carbon, it is handled by method similarly to Example 3.After processing, from purifying combination
Object separation silica dioxide gel simultaneously analyzes the composition other than oxide, and result is to form shown in table 2.
[table 1]
[table 2]
By embodiment 3~8 it is found that by making the purifying composition containing 1233yd and active carbon, aluminium oxide, zeolite
3A, zeolite 4A, zeolite 5A and silica dioxide gel contact, effectively can remove water, chloro- 3, the 3- bis- of 1- from purifying composition
Fluoro- 1- propine and HCFC-244ca.Particularly, it is known that when removing water with composition from purifying, use aluminium oxide, zeolite 3A, boiling
The effect of stone 4A, zeolite 5A or silica dioxide gel are good, when removing chloro- 3,3-, the bis- fluoro- 1- propine of 1- with composition from purifying, make
Effect with active carbon, aluminium oxide, zeolite 5A or silica dioxide gel is good.It is further known that being used when removing HCFC-244ca
Active carbon, aluminium oxide, zeolite 4A, the effect of zeolite 5A are good.
A possibility that being utilized in industry
1- through the invention chloro- 2, the manufacturing method of 3,3- trifluoro propenes, can efficiently from contain 1- chloro- 2,3,3-
The group of trifluoro propene and a kind or more of the compound selected from water, the fluoro- 1- propine of the chloro- 3,3- bis- of 1-, oxide and HCFC-244ca
It closes object and removes water, the fluoro- 1- propine of the chloro- 3,3- bis- of 1-, oxide and HCFC-244ca.
In addition, manufacturing method according to the invention, by carrying out above-mentioned 1- chloro- 2, the purifying of 3,3- trifluoro propenes can
Efficiently from containing the chloro- 2,3,3- trifluoro propene of 1- and selected from water, the fluoro- 1- propine of the chloro- 3,3- bis- of 1-, oxide and HCFC-
The composition of a kind or more of the compound of 244ca removes water, the fluoro- 1- propine of chloro- 3, the 3- bis- of 1-, oxide and HCFC-244ca,
So as to efficiently manufacture the chloro- 2,3,3- trifluoro propene of 1-.
Claims (8)
1.1- chloro- 2, the manufacturing method of 3,3- trifluoro propenes, which is characterized in that make containing 1- chloro- 2,3,3- trifluoro propenes and choosing
From the combination of at least one kind of compound of water, the fluoro- 1- propine of the chloro- 3,3- bis- of 1-, oxide and the chloro- 1,1,2,2- tetrafluoropropane of 3-
Object is contacted with solid absorbent, and the compound contained by the composition is removed.
2. 1- chloro- 2 as described in claim 1, the manufacturing method of 3,3- trifluoro propenes, which is characterized in that the solid absorption
Agent contains selected from at least one kind of of active carbon, zeolite, silica and aluminium oxide.
3. 1- chloro- 2 as claimed in claim 1 or 2, the manufacturing method of 3,3- trifluoro propenes, which is characterized in that the composition
Containing water, the solid absorbent contains at least one kind of to remove from the composition selected from zeolite, silica and aluminium oxide
The water.
4. 1- chloro- 2 according to any one of claims 1 to 3, the manufacturing method of 3,3- trifluoro propenes, which is characterized in that institute
It states composition and contains oxide, the solid absorbent contains at least one kind of with from the combination selected from active carbon and aluminium oxide
Object removes the oxide.
5. 1- chloro- 2 as described in any one of claims 1 to 4, the manufacturing method of 3,3- trifluoro propenes, which is characterized in that institute
Stating oxide is to be selected from the chloro- 2- of 3- (difluoromethyl) -2- fluoro ethylene oxide, bis- fluoracyl fluoride of 2,2-, formyl chloride, 1- chloro- 2,
Z formula body, the 3- of the fluoro- 1- peroxidating base -1- propylene of the chloro- 2,3,3- tri- of E formula body, 1- of the fluoro- 1- peroxidating base -1- propylene of 3,3- tri-
E formula body, the 1- of the fluoro- 3- peroxidating base -1- propylene of chloro- 1,1,2- tri-, the fluoro- 3- peroxidating base -1- propylene of the chloro- 2,3,3- tri- of 1-
At least one of the Z formula body of the fluoro- 3- peroxidating base -1- propylene of chloro- 2,3,3- tri-.
6. such as 1- according to any one of claims 1 to 5 chloro- 2, the manufacturing method of 3,3- trifluoro propenes, which is characterized in that institute
It states composition and contains the fluoro- 1- propine of chloro- 3, the 3- bis- of 1-, the solid absorbent contains selected from active carbon, silica and oxidation
Aluminium it is at least one kind of with from the composition remove the fluoro- 1- propine of the chloro- 3,3- bis- of 1-.
7. such as 1- according to any one of claims 1 to 6 chloro- 2, the manufacturing method of 3,3- trifluoro propenes, which is characterized in that institute
It states composition and contains 3- chloro- 1,1,2,2- tetrafluoropropane, the solid absorbent contains selected from active carbon, aluminium oxide, zeolite 4A
It is at least one kind of to remove the chloro- 1,1,2,2- tetrafluoropropane of 3- from the composition with zeolite 5A.
8. such as 1- according to any one of claims 1 to 7 chloro- 2, the manufacturing method of 3,3- trifluoro propenes, which is characterized in that also
Including making the chloro- 1,1,2,2- tetrafluoropropane of 3- that dehydrofluorination occur to manufacture containing the chloro- 2,3,3- trifluoro propene of 1- and choosing
From the combination of at least one kind of compound of water, the fluoro- 1- propine of the chloro- 3,3- bis- of 1-, oxide and the chloro- 1,1,2,2- tetrafluoropropane of 3-
The process of object.
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| 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 |
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| CN201780070437.4A Active CN109937196B (en) | 2016-11-15 | 2017-11-14 | Method for producing 1-chloro-2, 3, 3-trifluoropropene |
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| JP (1) | JP7003934B2 (en) |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114845982A (en) * | 2019-12-26 | 2022-08-02 | Ａｇｃ株式会社 | Method for producing 1-chloro-2, 3, 3-trifluoropropene |
| CN115023490A (en) * | 2020-01-31 | 2022-09-06 | Ａｇｃ株式会社 | Solvent composition, cleaning method, and method for producing coated article |
| 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 |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JPWO2021085134A1 (en) * | 2019-10-31 | 2021-05-06 | ||
| 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 |
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 |
| EP3925946A1 (en) * | 2013-03-15 | 2021-12-22 | Honeywell International, Inc. | Methods for removing halogenated ethylene impurities in 2,3,3,3-tetrafluoropropene product |
-
2017
- 2017-11-14 JP JP2018551649A patent/JP7003934B2/en active Active
- 2017-11-14 WO PCT/JP2017/040984 patent/WO2018092780A1/en active Application Filing
- 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 |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114845982A (en) * | 2019-12-26 | 2022-08-02 | Ａｇｃ株式会社 | Method for producing 1-chloro-2, 3, 3-trifluoropropene |
| CN115023490A (en) * | 2020-01-31 | 2022-09-06 | Ａｇｃ株式会社 | Solvent composition, cleaning method, and method for producing coated article |
| 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 |
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| Publication number | Publication date |
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| JP7003934B2 (en) | 2022-02-04 |
| CN109937196B (en) | 2022-08-16 |
| JPWO2018092780A1 (en) | 2019-10-17 |
| WO2018092780A1 (en) | 2018-05-24 |
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