CN105612139B - The purification process of 2,3,3,3 tetrafluoropropenes - Google Patents
The purification process of 2,3,3,3 tetrafluoropropenes Download PDFInfo
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- CN105612139B CN105612139B CN201480055614.8A CN201480055614A CN105612139B CN 105612139 B CN105612139 B CN 105612139B CN 201480055614 A CN201480055614 A CN 201480055614A CN 105612139 B CN105612139 B CN 105612139B
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- 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
- C07C17/383—Separation; Purification; Stabilisation; Use of additives by distillation
- C07C17/386—Separation; Purification; Stabilisation; Use of additives by distillation with auxiliary compounds
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Abstract
The present invention provides a kind of method for efficiently purifying HFO 1234yf from the mixture comprising 2,3,3,3 tetrafluoropropenes (HFO 1234yf) and the fluorochemical close with HFO 1234yf boiling point.HFO 1234yf purification process includes following process：(a) process for the distillation composition of 14 DEG C~30 DEG C of fluorochemical (wherein, except HFO 1234yf), HFO 1234yf and chloromethanes containing boiling point is prepared；(b) above-mentioned distillation is supplied into the process into the distillation for the cut for forming the Azeotrope compositions containing HFO 1234yf and chloromethanes or Azeotrope-like compositions with composition；And the process that (c) obtains the purifying HFO 1234yf higher than HFO 1234yf concentration in above-mentioned cut from above-mentioned cut.
Description
Technical field
The present invention relates to the purification process of 2,3,3,3- tetrafluoropropenes, more particularly to from comprising 2,3,3,3- tetrafluoropropenes and
The mixture of close fluorochemical efficiently purifies 2,3,3,3- tetrafluoropropenes with the boiling point of 2,3,3,3- tetrafluoropropenes
Method.
Background technology
The instead new refrigerant of greenhouse gases HFA 134a (HFC-134a), 2,3,3,3- tetrafluoros
Propylene (HFO-1234yf) is being sent to very big expectation in recent years.In this manual, for halogenated hydrocarbon, by the abbreviation of its compound
Note is in the bracket after chemical combination name, but in this manual as needed using its abbreviation to replace chemical combination name.
It is used as HFO-1234yf manufacture method, it is proposed that for example pass through from the raw material comprising chloro-fluoro-carbon kind with thermal decomposition
1 secondary response come the method that manufactures HFO-1234yf.As such method, for example, being proposed chloromethanes in patent document 1
(R40) and the mixture of dichlorodifluoromethane (R22) carries out heat resolve in the presence of thermal medium, to obtain HFO-1234yf's
Method.
In such reaction with thermal decomposition, it is known that in addition to generating target substance HFO-1234yf, be used as pair
Product also generates a variety of similar compounds.Generally, carry out removing by-product from reaction product by distilling using boiling-point difference
The operation of thing, for known 3,3,3- trifluoro propene (HFO-1243zf) (references with HFO-1234yf formation Azeotrope compositions
Patent document 2), the compound close with HFO-1234yf boiling point, it is difficult to removed with general destilling tower, it is necessary to one kind by it
The method that efficiently removes.
On the other hand, HFO-1234yf and hydrogen fluoride formation Azeotrope compositions and azeotrope-like group have been recorded in patent document 3
Compound, the technology for being separated HFO-1234yf and 1,1,1,2,2- pentafluoropropane (HFC-245cb) by azeotropic distillation using this.
Additionally, it is known that HFC-245cb is the initiation material for being used to manufacture HFO-1234yf for utilizing gas phase dehydrofluorination, in order to separate
Reaction product in the HFO-1234yf that includes and unreacting material HFC-245cb and use above-mentioned isolation technics.
But, it is necessary to which destilling tower and pipe arrangement will be included when using the composition comprising hydrogen fluoride to carry out azeotropic distillation
Whole distillation equipments to be made load in resistance to hydrogen fluoride specification, device side big, and operation is also not easy, and is deposited in terms of efficiency
In problem.
Prior art literature
Patent document
Patent document 1：No. 5201284 publication of Japanese Patent Laid
Patent document 2：Japanese Patent Laid 2012-508306 publications
Patent document 3：Japanese Patent Laid 2009-513719 publications
The content of the invention
The technical problems to be solved by the invention
The present invention is completed based on above-mentioned viewpoint, the purpose is to provide it is a kind of from comprising 2,3,3,3- tetrafluoropropenes and
The mixture of close fluorochemical efficiently purifies 2,3,3,3- tetrafluoropropenes with the boiling point of 2,3,3,3- tetrafluoropropenes
Method.
Solve the technical scheme that technical problem is used
The present invention, which is provided, includes following (a) process to the 2,3,3,3- tetrafluoropropenes (HFO-1234yf) of (c) process
Purification process.
(a) steaming for -14 DEG C~-30 DEG C of fluorochemical, HFO-1234yf, chloromethanes (R40) containing boiling point is prepared
The process with composition is evaporated, wherein, the fluorochemical does not include HFO-1234yf；
(b) distillation is supplied with composition to Azeotrope compositions of the formation comprising HFO-1234yf and R40 or class and be total to
Process in the distillation for the cut for boiling composition；And
(c) the purifying HFO-1234yf higher than HFO-1234yf concentration in cut work is obtained from the cut
Sequence.
In addition, in this specification, unless otherwise specified, the boiling point of compound means that normal pressure (1.013 × 105Pa)
Under boiling point.
Invention effect
In accordance with the invention it is possible to from the fluorochemical close comprising HFO-1234yf and with HFO-1234yf boiling point
Mixture efficiently purifies HFO-1234yf.
Embodiment
Below, embodiments of the present invention are illustrated.
The HFO-1234yf of present invention purification process is that purpose is from comprising HFO-1234yf and and HFO-1234yf
(boiling point:- 29 DEG C) the close compound of boiling point, specifically, boiling point for -14 DEG C~-30 DEG C fluorochemical (still,
Except HFO-1234yf, hereinafter also referred to fluorochemical (A)) purifying mixture HFO-1234yf method, and this method
It is following (a) process using the azeotropic distillation based on HFO-1234yf and R40 azeotropic to the purifying side of (c) process
Method.
(a) process for preparing the distillation composition containing fluorochemical (A), HFO-1234yf and R40 is (following to be also referred to as
For " distillation preparatory process ")；
(b) distillation is supplied with composition to Azeotrope compositions of the formation comprising HFO-1234yf and R40 or class and be total to
Process (hereinafter also referred to " azeotropic distillation process ") in the distillation for the cut for boiling composition；
(c) process that the purifying HFO-1234yf higher than HFO-1234yf concentration in the cut is obtained from the cut
(hereinafter also referred to " enrichment process ").
According to the purification process of the HFO-1234yf of the invention comprising above-mentioned (a) process to (c) process, by common
Distillation etc. can be from mixture (hereinafter also referred to " the thick HFO- comprising HFO-1234yf and fluorochemical (A) for being difficult to separate
1234yf ") efficiently separate HFO-1234yf and fluorochemical (A).That is, according to the purification process of the present invention, it can make
HFO-1234yf (also is indicated as " HFO- below relative to the ratio of the fluorochemical (A) in the purifying HFO-1234yf of gained
1234yf/ fluorochemicals (A) ") it is higher than HFO-1234yf/ fluorochemicals (A) in thick HFO-1234yf.
In other words, the purifying HFO-1234yf in this specification refers to：In the pass with the thick HFO-1234yf of following explanation
In system, HFO-1234yf/ fluorochemicals (A) in the purifying HFO-1234yf of gained are than in the thick HFO-1234yf that uses
The high mixture comprising HFO-1234yf of HFO-1234yf/ fluorochemicals (A) or HFO-1234yf sterlings.
In addition, in the method for the present invention, in the case that thick HFO-1234yf contains R40, thick HFO-1234yf is directly made
Used for distillation with composition, or thick HFO-1234yf is without in the case of R40, by adding R40 in thick HFO-1234yf
And as distillation composition, so as to implement the azeotropic distillation based on HFO-1234yf and R40 azeotropic.Any of the above-described situation
Under, distillation is equal to the HFO-1234yf/ in thick HFO-1234yf with the HFO-1234yf/ fluorochemicals (A) in composition
Fluorochemical (A).
Therefore, according to the purification process of the present invention, it may be said that can contain the HFO-1234yf/ in purifying HFO-1234yf
Fluorine compounds (A) are higher than the HFO-1234yf/ fluorochemicals (A) in distillation composition.According to the manufacturer of the present invention
Method, can be efficiently obtained purifying HFO-1234yf from the mixture comprising HFO-1234yf and fluorochemical (A).
Here, HFO-1234yf and R40 azeotropic is the phenomenon not previously known, the inventors discovered that the new phenomenon is simultaneously
It is applied to the purification process of the present invention.That is, generation is carried out inventors investigated a kind of and HFO-1234yf azeotropic compound
For load and unworkable hydrogen fluoride is caused to equipment etc., the load that the compound is caused to equipment etc. is few and also easily grasps
Make.As a result, confirming that R40 meets above-mentioned condition, and the R40 and HFO-1234yf of gained Azeotrope compositions or azeotrope-like
Composition seethes with excitement at a temperature of the low boiling point than any one of HFO-1234yf and R40, i.e. minimum azeotrope.
Take this, realizing makes to deposit in the mixture comprising HFO-1234yf and the compound close with HFO-1234yf boiling point
In R40, i.e., be free of R40 directly as distillatory composition, in the mixture in the case where the mixture includes R40
In the case of add R40 and as distillatory composition, carry out azeotropic distillation, make HFO-1234yf from said composition
It is that Azeotrope compositions or Azeotrope-like compositions are separated, then separates HFO-1234yf from the Azeotrope compositions or Azeotrope-like compositions
HFO-1234yf of the invention purification process.Hereinafter, to HFO-1234yf and R40 Azeotrope compositions or azeotrope-like combination
Thing is illustrated.
Azeotrope compositions are defined as follows：The gas phase generated by the gasification of liquid phase is with identical with the liquid phase of gasification
Composition composition, or the liquid phase generated by the liquefaction of gas phase be with liquefied gas phase identical constitute group
Compound.Therefore, composition of the Azeotrope compositions when evaporating, condensing repeatedly does not change, and can not be steamed with the change of composition
Evaporate and/or flow back.Using in the composition and gas phase in liquid phase composition it is equal, i.e. than volatility be 1.00 composition be used as azeotropic group
The composition of compound and calculate.But, the composition of Azeotrope compositions can change with pressure condition.
The composition being made up of HFO-1234yf and R40 is rubbed under conditions of gauge pressure 0.5MPa using HFO-1234yf as 57
The composition azeotropic that your %, R40 are 43 moles of %.The HFO-1234yf and R40 azeotropic composition is the condition in gauge pressure 0.5MPa
Under, the ratio volatility that is represented using following formula (1) as 1.00 composition, calculate in the following way.In addition, HFO-1234yf and
The boiling point of R40 Azeotrope compositions is 18.0 DEG C under pressure gauge pressure 0.5MPa.
(calculating the formula than volatility)
Than volatility=(mole % of the R40 in mole %/gas phase portion of the HFO-1234yf in gas phase portion)/(liquid phase
Mole % of R40 in mole %/liquid phase portion of HFO-1234yf in portion) ... (1)
In the autoclave with pressure gauge that the HFO-1234yf of composition requirement and R40 mixture is put into 500mL, with table
Pressure pressure reaches that 0.5MPa condition is slowly heated by external heater.Gauge in autoclave reaches 0.5MPa
After kept for certain time, after making composition in autoclave stable, sample is taken from gas phase and liquid phase.Each examination to gas phase and liquid phase
HFO-1234yf and R40 in sample are analyzed with gas chromatograph, obtain the group of the HFO-1234yf and R40 in each sample
Into.Obtained composition is substituted into above-mentioned formula (1), volatility is compared in calculating.
The operation is carried out by changing the HFO-1234yf put into the mixture in autoclave and R40 composition, is counted
Composition when calculation is 1.00 than volatility, azeotropic composition when obtaining gauge pressure for 0.5MPa.In addition, the HFO-1234yf under normal pressure
It can be calculated as below with R40 azeotropic composition：The experiment value and known thermodynamics constituted by using azeotropic obtained above is special
Property or Computational Thermodynamics characteristic simulated experiment, the content ratio for calculating the HFO-1234yf of liquid side is 57 moles of %, R40
Content ratio is 43 moles of %.In addition, the boiling point that can calculate HFO-1234yf and R40 Azeotrope compositions is -32 at ambient pressure
℃。
Here, generally in the composition for forming azeotropic composition, constitute the composition approximate with azeotropic composition and be used as table
Now close to azeotropic movement Azeotrope-like compositions.That is, Azeotrope-like compositions have what is be not classified in evaporation or condensation
Tendency, the composition of the gas phase generated by the gasification of liquid phase is roughly the same with the composition of the liquid phase of gasification, or passes through gas phase
Liquefaction and the liquid phase that generates composition it is roughly the same with the composition of liquefied gas phase.Therefore, Azeotrope-like compositions can be in group
Into hardly change in the case of distillation and/or flow back.
As the compositing range of HFO-1234yf and R40 Azeotrope-like compositions, specifically, preferably in common distillation
Under the conditions of, the scope of said composition distillation and/or backflow in the case where composition has almost no change.Composition is being constituted almost
The ratio volatility that distillation and/or the compositing range flowed back may be designated as example under defined pressure in the case of not changing reaches
To 1.00 ± α scope.
As the compositing range of HFO-1234yf and R40 Azeotrope-like compositions, specifically, preferably in defined pressure
It is lower reached than volatility 1.00 ± 0.20 scope.Under defined pressure, such as reached under gauge pressure 0.5MPa than volatility
1.00 ± 0.20 HFO-1234yf and R40 compositing range are same when above-mentioned azeotropic is constituted with calculating, can be by one side in table
Gradually change HFO-1234yf and R40 composition under conditions of pressure 0.5MPa while to determine two compounds in gas phase and liquid phase
Mole % calculate.
The HFO-1234yf for the scope that ratio volatility under the gauge pressure 0.5MPa calculated by this method is 1.00 ± 0.20
With the composition of R40 Azeotrope-like compositions, " HFO-1234yf/ (also is indicated as with HFO-1234yf and R40 mol ratio below
R40 ") scope be calculated as 41/59~85/15.In addition, under conditions of gauge is 0.5MPa, by above-mentioned compositing range
The boiling point for the Azeotrope-like compositions that HFO-1234yf and R40 is constituted is 18~19 DEG C.
In addition, the HFO-1234yf and R40 for the scope that the ratio volatility under normal pressure is 1.00 ± 0.20 azeotrope-like combination
The compositing range of thing is calculated as follows：By using the experiment of the composition of Azeotrope-like compositions during gauge pressure 0.5MPa obtained above
The simulated experiment of value and known thermodynamic behaviour or Computational Thermodynamics characteristic, calculates the HFO-1234yf/R40 of liquid side model
Enclose for 46/54~73/27.In addition, can calculate at ambient pressure, the class that is made up of the HFO-1234yf and R40 of above-mentioned compositing range
The boiling point of Azeotrope compositions is -31~-32 DEG C.
Similarly, by using the known thermodynamic behaviour or the mould of Computational Thermodynamics characteristic under various pressure (gauge pressure)
Draft experiment, has calculated HFO-1234yf and R40 azeotropic composition and the compositing range of Azeotrope-like compositions.By its result and normal pressure
It is shown in Table 1 together with gauge pressure 0.5MPa result.In addition, Azeotrope-like compositions are substantially equal with above-mentioned Azeotrope compositions
Treat on ground.In the following description, Azeotrope-like compositions are recited as including the composition of Azeotrope compositions.
[table 1]
Hereinafter, to the HFO- of the invention using the property by HFO-1234yf and the R40 Azeotrope-like compositions constituted
The each operation of 1234yf purification process is illustrated.
(a) preparatory process is distilled
(a) process is the process for preparing the distillation composition containing fluorochemical (A), HFO-1234yf and R40.
The purification process of the present invention can make the thick HFO-1234yf for comprising at least fluorochemical (A) and HFO-1234yf
For object.The purification process of the present invention is compared with as the thick HFO-1234yf of purifying object, to obtain fluorochemical (A) phase
The method for the purifying HFO-1234yf that ratio for HFO-1234yf is reduced.
Fluorochemical (A) is the fluorochemical (still, except HFO-1234yf) that boiling point is -14~-30 DEG C, can example
In the unreacted reactant or manufacturing process of the raw material that citing is used when such as manufacturing HFO-1234yf by known manufacture method
Intermediate, accessory substance of generation etc..In addition, being used as the thick HFO-1234yf for including fluorochemical (A) and HFO-1234yf, tool
Body can enumerate by reaction product obtained by known manufacture method manufacture HFO-1234yf or it is used to common side
Thick purified etc. obtained by method purifying.
As fluorochemical (A), 3, the 3- difluoropropenes that respective boiling point is shown in table 2 can be specifically enumerated
(HFO-1252zf), dicholorodifluoromethane (CFC-12), hexafluoropropene (HFP), CTFE (CTFE), Hexafluoro acetone, six
Fluorine expoxy propane (HFPO), 1,1,1,2- HFC-134as (HFC-134a), 1,2- difluoroethylenes (Z) (HFO-1132 (Z)), 1-
Chloro- 1- PVFs (HCFO-1131a), 3,3,3- trifluoro propenes (HFO-1243zf), 1,1- Difluoroethanes (HFC-152a), 1-
Chloro- 1- fluoroethanes (HFC-151a), 1- fluoropropenes (Z/E) (HFC-1261ze (Z/E)), 2- fluoropropenes (HFC-1261yf), 1,
1,2,2- HFC-134as (HFC-134), 1,1,2,3,3- pentafluoropropenes (HFO-1225yc), 1,1,3,3,3- pentafluoropropenes
(HFO-1225zc), 1,2,3,3,3- pentafluoropropenes (Z/E) (HFO-1225ye (Z/E)), 1,3,3,3- tetrafluoropropenes (Z/E)
(HFO-1234ze (Z/E)), 1,1,1,2,2- pentafluoropropanes (HFC-245cb), the chloro- 2,2- difluoroethylenes (HCFO-1122) of 1-,
At least the one of 1,1,1,2,3,3,3- heptafluoro-propanes (HFC-227ea) and 1,1,1,2,2,3,3- heptafluoro-propanes (HFC-227ca)
Kind.
In addition, in fluorochemical (A), the compound with the mark such as (Z) or (E) represents geometry after chemical combination name
Isomers Z bodies or E bodies.In addition, in table 2, for the compound with geometric isomer, the boiling point of E bodies and Z bodies is indistinguishable
In the case of, it is expressed as after chemical combination name (Z/E).
[table 2]
As long as boiling point as shown in table 2 is -14~-30 DEG C of fluorochemical (A), then with HFO-1234yf and R40
Azeotrope-like compositions boiling spread boiling-point difference enough, the Azeotrope-like compositions with HFO-1234yf and R40 can be realized
Fractionation.In addition, the boiling point of the boiling point of fluorochemical (A) and HFO-1234yf (- 29 DEG C) is close, reach by common
Distillation can not segregative degree, this is favourable in terms of purification efficiency.
In addition, for fluorochemical (A), in the case of fluorochemical (A) of the boiling point for -19~-30 DEG C, this hair
The effect of purification efficiency correlation in bright method becomes apparent from, in situation of the boiling point for -19~-28 DEG C of fluorochemical (A)
Under, the effect of the purification efficiency correlation in method of the invention is particularly evident.
In addition, containing the change that the boiling point beyond fluorochemical (A) is -14~-30 DEG C for example in thick HFO-1234yf
In the case of compound, point with HFO-1234yf and R40 Azeotrope-like compositions can be realized in the same manner as fluorochemical (A)
Evaporate.
As such compound, such as diazomethane (CH can be enumerated2-N2, -23 DEG C), dimethylsilane (CH3-SiH2-
CH3, -22 DEG C), dicyan (NC-CN, -21 DEG C), ethynylmethyl ether (CH ≡ C-O-CH3, -17 DEG C), vinyl chloride (CH2=
CHCl, -14 DEG C), chloroacetylene (Cl-C ≡ C-H, -30 DEG C), methyl ether (CH3-O-CH3, -24 DEG C), formaldehyde (H-C (O)-H, -19 DEG C)
Deng.
In addition, except the chemical combination beyond the region of objective existence comprising the boiling point with -14 DEG C~-30 DEG C in thick HFO-1234yf, also comprising tool
In the case of the compound for the boiling point for having more than -14 DEG C, for these compounds, it can also be realized by the purification process of the present invention
With HFO-1234yf separation.
In addition, in patent document 1, HFO-1243zf and HFO-1234yf azeotropic, the boiling point of the Azeotrope-like compositions is about
It it is about -30 DEG C~about 66 DEG C under 14psia~about 230psia (about 0.1MPa~about 1.6MPa).But, including HFO-
In the distillation composition of 1243zf, HFO-1234yf and R40 method using the present invention, HFO-1234yf and R40 are formed
Cut comprising such azeotropic compound, can be fractionated by Azeotrope-like compositions by common distillation, so easily by HFO-
1234yf and HFO-1243zf separation.Because：The boiling point of HFO-1234yf and R40 Azeotrope-like compositions compares HFO-
The boiling point of 1234yf and HFO-1243zf Azeotrope-like compositions is lower.
Here, prepare distillation in (a) process is included with composition：For example in HFO-1234yf described above manufacture
During in obtained thick HFO-1234yf, it is in the case that the thick HFO-1234yf includes R40, the thick HFO-1234yf is direct
It is used as distillation composition.In addition, similarly, in the case that thick HFO-1234yf does not include R40, by thick HFO-1234yf
Middle addition R40 prepares distillation composition.
To the fluorochemical (A) contained by the distillation composition for preparing in (a) process, HFO-1234yf and R40
Respective content is not particularly limited.In the purification process of the present invention, by the distillation of (b) process, by distillation composition shape
Into HFO-1234yf and R40 Azeotrope-like compositions, the cut comprising the Azeotrope-like compositions is fractionated.Here, used in distillation
The Azeotrope-like compositions can be formed in composition containing HFO-1234yf and R40 in any proportion.Therefore, in (a) process
The distillation of preparation is not particularly limited with the HFO-1234yf in composition and R40 respective content.
But, will preferably in (b) process in order to which distillation is efficiently purified with the HFO-1234yf contained by composition
Distillation is fractionated with the substantially the entirety of amount of the HFO-1234yf in composition as the cut comprising Azeotrope-like compositions.
Therefore, distillation with the HFO-1234yf/R40 in composition be preferably as defined in azeotrope-like combination under distillation pressure
Below the HFO-1234yf/R40 of the thing upper limit, more preferably below the HFO-1234yf/R40 of Azeotrope compositions.If HFO-
Below the upper limits of the 1234yf/R40 for the HFO-1234yf/R40 of the Azeotrope-like compositions under the pressure, then it can be steamed common
Evaporate and divided distillation with the substantially the entirety of amount of the HFO-1234yf in composition as the cut comprising Azeotrope-like compositions
Evaporate.
If in addition, HFO-1234yf/R40 is below the HFO-1234yf/R40 of Azeotrope compositions, will can distill
More efficiently separated with the HFO-1234yf in composition into the cut comprising Azeotrope-like compositions.As known from Table 1, class is formed
The HFO-1234yf/R40 of Azeotrope compositions higher limit 99/1 is value when pressure is 1.3~3.0MPaG, for example, be in pressure
In the case of 0.5MPaG, the higher limit for forming the HFO-1234yf/R40 of Azeotrope-like compositions is 85/15, is at ambient pressure 73/
27.So, in the case where being difficult to high pressure setting according to ability of destilling tower used in (b) process etc., preferably calculate
The HFO-1234yf/R40 of formation Azeotrope-like compositions under possible setting pressure higher limit, so that in distillation composition
HFO-1234yf/R40 reach that the condition below the higher limit is adjusted.
The pressure limit distilled generally is calculated as 0~3.0MPa or so with gauge pressure, and (following, pressure is the situation of gauge pressure
Under, it is labeled as " G " after unit).In addition, in 0~3.0MPaG pressure limit, forming the composition model of Azeotrope-like compositions
Enclose as shown in table 1,26/74~99/1 is calculated as with HFO-1234yf/R40, the compositing range for forming Azeotrope compositions is 57/43
(about 1.33).
Therefore, distillation with HFO-1234yf of the amount relative to 1 mole of the R40 in composition be preferably 0.01 mole with
On, more preferably more than 0.1 mole, further preferred more than 0.2 mole, most preferably particularly preferred more than 0.5 mole, 0.75 mole
More than.Take this, can reduce because do not formed Azeotrope-like compositions superfluous HFO-1234yf be fractionated for comprising class
HFO-1234yf caused by the different cut (cut for usually including fluorochemical (A)) of the cuts of Azeotrope compositions
Loss.
Even in addition, as described above, the amount of the R40 in distillation composition is more azeotrope-like with HFO-1234yf than being formed
The superfluous amount of the amount of composition, also can form the cut for including Azeotrope-like compositions by distilling, so, can be as needed
Distillation is set greater than above-mentioned value with the amount of the R40 in composition.But, if it is considered that suppress because distillation with composition from
The load of reboiler and condenser, the R40 reduced in power consumption and suppression cost, distillation composition caused by the amount increase of body
HFO-1234yf of the amount relative to 1 mole be preferably less than 100 moles, more preferably less than 10 moles.
(a) in process, distillation composition can be carried out as follows preparation：For example, for the purifying side as the application present invention
The thick HFO-1234yf of the object of method, determines HFO-1234yf and R40 content, according to their content, with obtained distillation
With the HFO-1234yf/R40 of composition reach the condition of above-mentioned preferred scope added into the thick HFO-1234yf R40 or
Without.
In addition, the thick HFO-1234yf used in the present invention exceedes the group of above-mentioned preferred scope, i.e. Azeotrope-like compositions
In the case of into scope and excessively containing R40, as long as by the thick HFO-1234yf directly as distillation composition for (b) work
The distillation of sequence.In addition, in the present invention, distillation with composition not necessarily only by HFO-1234yf, fluorochemical (A) and
R40 is constituted.In the range of the effect of the present invention is not damaged, HFO-1234yf, fluorochemical (A) and R40 can also be included
Compound in addition.These compounds are generally to be brought into the form of included in thick HFO-1234yf in distillation composition
Compound.
It can be obtained by the following method as the thick HFO-1234yf of the application of the purification process of the present invention：For example from
F is produced with that can thermally decompose by R402C:The HFO-1234yf synthetic method of adjoint thermal decomposition of fluorochemical obtain
Reaction product in, by the cut that will be made up of HFO-1234yf, fluorochemical (A) and R40 mixture such as distilling
Or the fraction seperation using the mixture as principal component is obtained, above-mentioned fluorochemical be such as R22, tetrafluoroethene (TFE),
HFP, octafluorocyclobutane (RC318), CTFE, trifluoro-ethylene (HFO-1123), HFPO (HFPO) etc..
The thick HFO-1234yf obtained by the above-mentioned HFO-1234yf with thermal decomposition synthetic method can contain upper
State the whole fluorochemicals (A) shown in table 1.In addition, by thus obtained thick HFO-1234yf directly or addition R40
In the case of being used as distillation composition afterwards, as set forth above, it is possible to contain HFO- in the range of the effect for not damaging the present invention
Other compounds beyond 1234yf, fluorochemical (A) and R40.
As other compounds, R22, TFE, RC318, HFO-1123, HFPO, heptafluoro-propane, chlorine difluoro can be specifically enumerated
Ethene, 1,1- difluoroethylenes (HFO-1132a), vinyl chloride, chloro-tetrafluoroethane (HCFC-124), chlorofluoromethane (HCFC-31), two
Fluoromethane (HFC-32) etc..In addition, from the viewpoint of HFO-1234yf is efficiently purified, the content of other compounds is being steamed
Evaporate to use and 90 moles of %, more preferably less than 70 moles % are preferably less than in composition.The most of of other compounds are and HFO-
The big compound of the boiling-point difference of 1234yf and fluorochemical (A), before the purification process of the present invention is carried out, by common
Distillation can be easily separated in advance.
As the thick HFO-1234yf for the purification process that can be applied to the present invention, than that described above, can enumerate for example makes
The thick HFO-1234yf obtained when manufacturing HFO-1234yf with the isomer mixture of dichloro pentafluoropropane (HCFC-225).
The isomer mixture for using HCFC-225 as raw material is manufactured in HFO-1234yf method, makes 1 in raw material,
The chloro- 2,2,3,3,3- pentafluoropropanes (HCFC-225ca) of 1- bis- optionally dehydrofluorination to manufacture the chloro- 2,3,3,3- of 1,1- bis-
Tetrafluoropropene (CFO-1214ya), obtained CFO-1214ya is reduced, and manufactures HFO-1234yf.
Using the reaction product finally given as thick HFO-1234yf, in thick HFO-1234yf, fluorine-containing chemical combination is used as
Thing (A), can include following material：The chloro- 1,1,3,3,3- pentafluoropropanes (HCFC-225aa) of 2,2- bis- in feedstock composition are entered
Reduzate, the i.e. HFO-1243zf excessively of HFO-1225zc and HFO-1234yf obtained by being reduced after row dehydrochlorination reaction,
HFO-1252zf etc..
In addition, described in patent document 3 by HFC-245cb dehydrofluorinations with including obtained by manufacturing during HFO-1234yf
The reaction product of unreacting material etc. is can be applied to the thick HFO-1234yf of the purification process of the present invention.In this case,
HFC-245cb etc. can be included in thick HFO-1234yf in contained fluorochemical (A).
In addition, in the case that these thick HFO-1234yf are applied into the purification process of the present invention, the thick HFO-1234yf
Substantially free of R40, so adding the R40 of ormal weight in (a) process to prepare distillation composition.The thick HFO- used
1234yf and thick HFO-1234yf obtained by the synthetic method by the above-mentioned HFO-1234yf with thermal decomposition is it is also possible to wrap
Containing other compounds in addition to HFO-1234yf, fluorochemical (A) and R40.But, the contents of other compounds is to be made
Distillation represents with content during composition, preferably shorter than 90 moles %, more preferably less than 70 moles %.
(b) azeotropic distillation process
(b) process in the method for the present invention is that the distillation composition that will prepare in above-mentioned (a) process contains for being formed
Have HFO-1234yf and R40 Azeotrope-like compositions cut distillation in process.
(b) in the distillation in process, the distillation composition prepared above in above-mentioned (a) process is passed through, it is not necessary to especially
Condition, the condition setting, such as pressure limit in the distillation of usual scope are in the range of 0~3.0MPaG, and for temperature
Spend scope, make tower top temperature in the range of -32~88 DEG C by setting pressure, can be formed containing HFO-1234yf and
The distillation of the cut of R40 Azeotrope-like compositions.In addition, pressure condition is preferred to use 0 (normal pressure)~2.0MPaG, for temperature
Condition, it is preferred -32~68 DEG C as tower top temperature by setting pressure.Hereinafter, HFO-1234yf and R40 will can also be contained
The cuts of Azeotrope-like compositions be referred to as azeotropic cut.
(b) distillation of process, preferably with the amount of the HFO-1234yf in azeotropic cut relative in distillation composition
The ratio of HFO-1234yf amount reaches that 75 moles of more than % condition is carried out, more preferably 85 moles more than %, further preferably
95 moles of more than %, most preferably 99 moles more than %.Furthermore it is preferred that relative with the amount of the fluorochemical (A) in azeotropic cut
Reach that 50 moles of below % condition is distilled with the ratio of the amount of the fluorochemical (A) in composition in distillation, it is more excellent
Select 25 moles of below %, further preferred 15 moles of below %, most preferably 5 moles below %.Take this, can obtain higher purity
HFO-1234yf。
In order to meet above-mentioned condition, for example, from the case that tower top takes out azeotropic cut as distillate, preferably will
Tower top temperature is set to more than the boiling point of the Azeotrope-like compositions under distillation pressure, and column bottom temperature is set into fluorochemical (A)
Below boiling point.Tower top temperature is mainly adjusted by carry out above-mentioned operation.Now, by reducing tower top temperature and column bottom temperature
Difference, can lower the load of reboiler.In addition, reached by the boiling point with Azeotrope-like compositions near normal temperature, such as about -15
~50 DEG C of condition sets pressure, can reduce the load of reboiler.As such pressure, preferably 0.1~
1.3MPaG。
(b) process distillation can by using for example possess destilling tower, to the destilling tower supply distillation composition list
The distillation of unit first, that distillate is taken out from the tower top of the destilling tower and the unit of the bottom of towe taking-up tower bottom liquid from the destilling tower
Device is carried out.Can be the destilling tower of hollow destilling tower or multisection type as the destilling tower used.In addition, steaming
Evaporating can be carried out by batch-type, can also be carried out by continous way.
In the case where being distilled using the destilling tower of such as multisection type, generally above-mentioned steaming is supplied from the stage casing of destilling tower
Evaporate and use composition, above-mentioned azeotropic cut is obtained as the distillate of the tower top taking-up from destilling tower.In addition, above-mentioned distillation group
Cut (hereinafter also referred to fluorochemical (A) cut) contained by the fluorochemical (A) included in compound can be used as from tower
Bottom take out tower bottom liquid and separate.It is somebody's turn to do in addition, distillation is exceeded with the content ratio of the HFO-1234yf/R40 in composition
In the case of the scope of Azeotrope-like compositions under conditions of distillation, the HFO-1234yf or R40 excessively contained is contained with being contained in
Form in fluorine compounds (A) cut is separated as from the tower bottom liquid that bottom of towe is taken out.
In addition, in (b) process of the present invention, azeotropic cut is not limited to as distillate separation to take from tower top separation
Go out, as long as the column plate on the column plate supplied distillation with composition to tower, it is possible to azeotropic is evaporated from any column plate
It is allocated as taking out for distillate.Similarly, the reality of the invention for taking out fluorochemical (A) cut as tower bottom liquid from bottom of towe
The mode of applying is illustrated, but the present invention is not limited to this, as long as distillation is supplied with composition the column plate to tower it
Under column plate, it is possible to fluorochemical (A) cut is taken out as tower bottom liquid.
Because, as described above, the boiling point of the Azeotrope-like compositions of HFO-1234yf and R40 under such as normal pressure for-
31~-32 DEG C, in addition the boiling point of fluorochemical (A) be -14~-30 DEG C, HFO-1234yf boiling point be -29 DEG C, R40 boiling
Point is -24.2 DEG C.
In the case of HFO-1234yf being included in fluorochemical (A) cut, then by above-mentioned (a) process and (b) process,
HFO-1234yf can be separated from fluorochemical (A) cut., can be with the case of including R40 in fluorochemical (A) cut
In above-mentioned (a) process, distillation composition is prepared by being added in thick HFO-1234yf, and for (b) process,
So as to which R40 be separated from fluorochemical (A) cut.
In addition, by the way that distillation is adjusted into defined with the HFO-1234yf/R40 in composition in above-mentioned (a) process
The composition of Azeotrope-like compositions under distillation condition, is distilled with the defined distillation condition in (b) process, can be fractionated
It is for the azeotropic cut containing HFO-1234yf and R40 Azeotrope-like compositions and substantially fluorine-containing without HFO-1234yf or R40
Compound (A) cut.
Thus, the azeotropic cut of gained, by (c) process for after, HFO-1234yf is concentrated in (b) process.
In addition, the content ratio of the compound beyond HFO-1234yf and R40 in azeotropic cut is 90 relative to azeotropic cut total amount
Below quality %, preferably below 70 mass %, more preferably below 50 mass %.
(c) enrichment process
(c) process is that the azeotropic cut obtained from (b) process is obtained and the HFO-1234yf concentration in the azeotropic cut
Compare, the process for the purifying HFO-1234yf that HFO-1234yf concentration is improved.In addition, obtained purifying HFO-1234yf is as above
Defined is stated, compared with the HFO-1234yf/ fluorochemicals (A) in the thick HFO-1234yf used, with higher HFO-
1234yf/ fluorochemicals (A).
Here, scopes of the HFO-1234yf/R40 26/74~99/1 in the azeotropic cut obtained in above-mentioned (b) process
It is interior.The content of HFO-1234yf in the purifying HFO-1234yf obtained in this (c) process is relative to purifying HFO-1234yf's
Total amount is preferably more than 90 mass % more preferably more than 95 mass %, further preferred more than 99 mass %.
As the specific method of (c) process, it can use and be selected from transformation distillation, extractive distillation, azeotropic distillation, phase separation and film
At least one of separation partition method.These separation methods are used when being separated into by Azeotrope compositions and constituting compound logical
Normal method, during by the azeotropic cut obtained in (b) process for these separation methods, using conventional method.
Embodiment
Hereinafter, by embodiment, the present invention is described in detail.Example 1~6, example 8,10 are embodiments, and example 7, example 9 are ratios
Compared with example.The present invention is not limited to these embodiments.
[example 1~7]
In example 1~6, as distillation composition, prepare the table 3 for including HFO-1234yf, HFO-1243zf and R40 respectively
The distillation composition shown in~table 8.In example 7, as distillation composition, prepare only to include HFO-1234yf and HFO-
The distillation composition shown in 1243zf table 9.In example 1~7, from the destilling tower of the theoretical cam curve with 50 column plates
The 40th column plate supplies these distillation compositions with 1.0 mols/hr of flow to destilling tower from tower top, respectively with table 3~
Operating pressure [MPaG], tower top temperature [DEG C], the column bottom temperature [DEG C] shown in table 9 carries out continuous still.
In 1~example of example 7, respectively with the speed (yield total [mol/hr]) that is shown in 3~table of table 9 from tower top
Distillate is taken out, tower bottom liquid is taken out from bottom of towe.Each distillate, tower bottom liquid for taking-up are by gas chromatograph come analysis group
Into.The analysis result of the composition of distillate and tower bottom liquid in 1~example of example 7 is shown in Table 3 below~table 9.
According to obtained analysis result, for each composition in the distillation composition in 1~example of example 7, according to following formula
Calculate the rate of recovery of the composition relative to the composition in distillation composition in distillate, tower bottom liquid.
Component amount × 100 in component amount/distillation composition in the rate of recovery (%)=distillate or tower bottom liquid
In addition, calculate HFO-1234yf in distillation composition, distillate and tower bottom liquid relative to HFO-1234yf and
The ratio (mole %) of HFO-1243zf total amount.
Calculate HFO-1234yf and R40 total amount of the total amount relative to distillation composition, distillate and tower bottom liquid
Ratio (mole %).
Calculate the HFO-1234yf/R40 (mol ratio) in distillation composition, distillate and tower bottom liquid.By in each example
As a result it is shown in the lower column of 3~table of table 9.
[table 3]
[table 4]
[table 5]
[table 6]
[table 7]
[table 8]
[table 9]
The distillate obtained in 1~example of example 6 contains HFO-1234yf and R40 Azeotrope-like compositions, and its total content is
95.96~99.77 moles of %, are mixtures obtained by abundant removing HFO-1243zf.By being distilled selected from transformation, extracting steaming
Evaporate, azeotropic distillation, at least one partition method of phase separation and UF membrane, it is main from above-mentioned distillate to remove R40, purified
HFO-1234yf。
[example 8,9]
In example 8, as distillation composition, prepare what is shown in the table 10 comprising HFO-1234yf, HFC-152a and R40
Distillation composition.In example 9, as distillation composition, prepare the only table 11 comprising HFO-1234yf and HFC-152a and show
Distillation composition.In example 8,9, from the 40th column plate from tower top of the destilling tower of the theoretical cam curve with 50 column plates with
1.0 mols/hr of flow supplies these distillation compositions to destilling tower, respectively the operating pressure to be shown in table 10,11
[MPaG], tower top temperature [DEG C], column bottom temperature [DEG C] carry out continuous still.
In example 8,9, taken respectively with the speed (total [mol/hr] of yield) shown in table 10,11 from tower top
Go out distillate, tower bottom liquid is taken out from bottom of towe.Each distillate, tower bottom liquid for taking-up analyze composition by gas chromatograph.
The analysis result of the composition of distillate and tower bottom liquid in example 8,9 is shown in table 10 below, 11.
It is same with above-mentioned example 1 for each composition in the distillation composition in example 8,9 according to obtained analysis result
Ground calculates the rate of recovery of the composition relative to the composition in distillation composition in distillate, tower bottom liquid.
In addition, calculate HFO-1234yf in distillation composition, distillate and tower bottom liquid relative to HFO-1234yf and
The ratio (mole %) of HFC-152a total amount.
Calculate HFO-1234yf and R40 total amount of the total amount relative to distillation composition, distillate and tower bottom liquid
Ratio (mole %).
Calculate the HFO-1234yf/R40 (mol ratio) in distillation composition, distillate and tower bottom liquid.By in each example
As a result in the lower column for being shown in table 10,11.
[table 10]
[table 11]
The distillate obtained in example 8 contains HFO-1234yf and R40 Azeotrope-like compositions, and its content ratio is 99.40
Mole %, is abundant to remove mixture obtained by HFC-152a.By being distilled selected from transformation, extractive distillation, azeotropic distillation, phase point
It is main from above-mentioned distillate to remove R40 from least one partition method with UF membrane, obtain purifying HFO-1234yf.
[example 10]
As distillation composition, prepare comprising the various fluorochemicals (A) shown in HFO-1234yf and table 12 and
The distillation composition shown in R40 table 12.From the destilling tower of the theoretical cam curve with 50 column plates the 40th from tower top
Column plate supplies the distillation composition with 1.0 mols/hr of flow to destilling tower, with the operating pressure shown in table 12
[MPaG], tower top temperature [DEG C], column bottom temperature [DEG C] carry out continuous still.
Distillate is taken out from tower top with the speed (total [mol/hr] of yield) shown in table 12, taken from bottom of towe
Go out tower bottom liquid.Each distillate, tower bottom liquid for taking-up analyze composition by gas chromatograph respectively.Distillate in example 10
It is shown in the analysis result of the composition of tower bottom liquid in table 1 below 2.
According to obtained analysis result, for each composition in the distillation composition in example 10, in the same manner as above-mentioned example 1
Calculate the rate of recovery of the composition relative to the composition in distillation composition in distillate, tower bottom liquid.
In addition, calculate HFO-1234yf in distillation composition, distillate and tower bottom liquid relative to HFO-1234yf and
The ratio (mole %) of the total amount of fluorochemical (A).
Calculate HFO-1234yf and R40 total amount of the total amount relative to distillation composition, distillate and tower bottom liquid
Ratio (mole %).
Calculate the HFO-1234yf/R40 (mol ratio) in distillation composition, distillate and tower bottom liquid.Show the result in
In the lower column of table 12.
[table 12]
The distillate obtained in example 10 contains HFO-1234yf and R40 Azeotrope-like compositions, and its content ratio is 99.74
Mole %, is abundant to remove mixture obtained by fluorochemical (A).By being distilled selected from transformation, extractive distillation, azeotropic steam
Evaporate, be separated and UF membrane at least one partition method, it is main from above-mentioned distillate to remove R40, obtain purifying HFO-
1234yf。
Utilization possibility in industry
In accordance with the invention it is possible to from the fluorochemical close comprising HFO-1234yf and with HFO-1234yf boiling point
Mixture efficiently purifies HFO-1234yf, so present invention may effectively utilize various thick in what is produced from extensive field
HFO-1234yf obtains the HFO-1234yf of high-purity.
In addition, quoting the explanation for the Japanese patent application 2013-211748 filed an application on October 9th, 2013 herein
Book, claims, accompanying drawing and summary all the elements as description of the invention announcement.
Claims (6)
- The purification process of 1.2,3,3,3- tetrafluoropropenes, it includes：(a) prepare the distillation containing boiling point for -14 DEG C~-30 DEG C of fluorochemical, 2,3,3,3- tetrafluoropropenes, chloromethanes to use The process of composition, wherein, the fluorochemical does not include 2,3,3,3- tetrafluoropropenes and chloromethanes；(b) by the distillation supplied with composition to formed the Azeotrope compositions comprising 2,3,3,3- tetrafluoropropenes and chloromethanes or Process in the distillation of the cut of Azeotrope-like compositions；And(c) the purifying 2,3,3,3- tetrafluoro third higher than 2,3,3,3- tetrafluoropropene concentration in the cut is obtained from the cut The process of alkene；The amount of 2,3,3,3- tetrafluoropropenes in the cut is relative to the 2,3,3,3- tetrafluoros third in the distillation composition The ratio of the amount of alkene is 75 moles of more than %, and the amount of the fluorochemical in the cut distills use relative to described The ratio of the amount of the fluorochemical in composition is 50 moles of below %；Described 2 relative to 1 mole, 3,3,3- tetrafluoropropenes, the distillation is with the amount of the chloromethanes in composition 0.01~100 mole；The fluorochemical is to be selected from 3,3- difluoropropenes, dicholorodifluoromethane, hexafluoropropene, CTFE, 1,1,1, The chloro- 1- PVFs of 2- HFC-134as, 1-, Z-1,2- difluoroethylenes, 3,3,3- trifluoro propenes, 1,1- Difluoroethanes, the chloro- 1- fluorine of 1- Ethane, 1,1,2,2- HFC-134as, 1,1,3,3,3- pentafluoropropenes, 1,1,2,3,3- pentafluoropropenes, Z/E-1,2,3,3,3- five Fluoropropene, Z/E-1,3,3,3- tetrafluoropropenes, 1,1,1,2,2- pentafluoropropanes, Z/E-1- fluoropropenes, 2- fluoropropenes, hexafluoro third Ketone, 1,1,1,2,3,3,3- heptafluoro-propanes, 1,1,1,2,2,3,3- heptafluoro-propanes, HFPO and the chloro- 2,2- difluoros of 1- At least one of ethene.
- 2. as claimed in claim 12, the purification process of 3,3,3- tetrafluoropropenes, it is characterised in that (c) process passes through The cut is supplied to being distilled selected from transformation, extractive distillation, azeotropic distillation, phase separation and at least one separation of UF membrane Method is carried out.
- 3. as claimed in claim 12, the purification process of 3,3,3- tetrafluoropropenes, it is characterised in that the distillation composition In fluorochemical boiling point be -19 DEG C~-30 DEG C.
- 4. as claimed in claim 12, the purification process of 3,3,3- tetrafluoropropenes, it is characterised in that the Azeotrope compositions or The Azeotrope-like compositions seethe with excitement at a temperature of than the low boiling point of any of chloromethanes and 2,3,3,3- tetrafluoropropenes.
- 5. 2 as described in claim 1 or 3, the purification process of 3,3,3- tetrafluoropropenes, it is characterised in that the distillation group Compound is obtained by adding chloromethanes into the composition comprising 2,3,3,3- tetrafluoropropenes in (a) process.
- 6. the purification process as described in claim 1 or 3, it is characterised in that the distillation with composition be by chloromethanes and Can thermally decompose and produce the adjoint thermal decomposition of the fluorochemical of difluorocarbene 2,3,3,3- tetrafluoropropenes manufacture reaction and The distillation fraction of the reaction product obtained.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2013-211748 | 2013-10-09 | ||
| JP2013211748 | 2013-10-09 | ||
| PCT/JP2014/076995 WO2015053339A1 (en) | 2013-10-09 | 2014-10-08 | Method for purifying 2,3,3,3-tetrafluoropropene |
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| CN105612139B true CN105612139B (en) | 2017-09-19 |
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| EP2939994B1 (en) * | 2012-12-27 | 2018-07-18 | Asahi Glass Company, Limited | Method for purifying tetrafluoropropene |
| TWI695423B (en) | 2014-06-18 | 2020-06-01 | 法商液態空氣喬治斯克勞帝方法研究開發股份有限公司 | Chemistries for tsv/mems/power device etching |
| JP6102984B2 (en) * | 2015-05-29 | 2017-03-29 | ダイキン工業株式会社 | Method for producing fluorine-containing compound |
| FR3046163B1 (en) * | 2015-12-23 | 2019-12-13 | Arkema France | PROCESS FOR THE PRODUCTION AND PURIFICATION OF 2,3,3,3-TETRAFLUORO-1-PROPENE. |
| EP3402771B1 (en) | 2016-01-14 | 2021-07-28 | Srf Limited | Process for the preparation of olefin containing fluorine |
| US10233137B1 (en) * | 2017-10-13 | 2019-03-19 | Honeywell International Inc. | Method for removing unsaturated halogenated impurities from 2,3,3,3-tetrafluoropropene (HFO-1234yf) |
| JP2021523884A (en) * | 2018-05-16 | 2021-09-09 | エスアールエフ リミテッド | Methods for Purification of Olefin Supplies Containing 1234yf |
| EP4100482A2 (en) * | 2020-02-07 | 2022-12-14 | The Chemours Company FC, LLC | Compositions comprising 2,3,3,3 tetrafluoropropene and methods for making and using the compositions |
| CN111253211B (en) * | 2020-03-16 | 2022-08-05 | 天津绿菱气体有限公司 | Separation and purification method of high-purity electronic-grade tetrafluoropropene HFO-1234yf |
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| US2931840A (en) * | 1958-11-25 | 1960-04-05 | Du Pont | Process for preparing 2, 3, 3, 3-tetrafluoropropene |
| CN1969027A (en) * | 2004-04-16 | 2007-05-23 | 霍尼韦尔国际公司 | Azeotrope-like compositions of difluoromethane and trifluoroiodomethane |
| CN102442880A (en) * | 2011-10-22 | 2012-05-09 | 山东东岳高分子材料有限公司 | Preparation method of 2, 3, 3, 3-tetrafluoropropene |
| US20120151959A1 (en) * | 2009-09-11 | 2012-06-21 | Arkema France | Binary refrigerating fluid |
| CN103328424A (en) * | 2011-02-04 | 2013-09-25 | 旭硝子株式会社 | Method for purifying 2,3,3,3-tetrafluoropropene |
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| JP5122945B2 (en) * | 2004-04-16 | 2013-01-16 | ハネウェル・インターナショナル・インコーポレーテッド | An azeotrope-like composition of tetrafluoropropene and trifluoroiodomethane |
| JP5149456B1 (en) * | 2012-03-14 | 2013-02-20 | 旭硝子株式会社 | Process for producing 2,3,3,3-tetrafluoropropene and 1,1-difluoroethylene |
| JP5201284B1 (en) * | 2012-03-14 | 2013-06-05 | 旭硝子株式会社 | Method for producing 2,3,3,3-tetrafluoropropene |
| JP6102917B2 (en) * | 2012-04-09 | 2017-03-29 | 旭硝子株式会社 | Azeotropic or azeotrope-like composition and method for producing 2,3,3,3-tetrafluoropropene or chloromethane |
-
2014
- 2014-10-08 JP JP2015541622A patent/JP6358263B2/en not_active Expired - Fee Related
- 2014-10-08 WO PCT/JP2014/076995 patent/WO2015053339A1/en active Application Filing
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| US2931840A (en) * | 1958-11-25 | 1960-04-05 | Du Pont | Process for preparing 2, 3, 3, 3-tetrafluoropropene |
| CN1969027A (en) * | 2004-04-16 | 2007-05-23 | 霍尼韦尔国际公司 | Azeotrope-like compositions of difluoromethane and trifluoroiodomethane |
| US20120151959A1 (en) * | 2009-09-11 | 2012-06-21 | Arkema France | Binary refrigerating fluid |
| CN103328424A (en) * | 2011-02-04 | 2013-09-25 | 旭硝子株式会社 | Method for purifying 2,3,3,3-tetrafluoropropene |
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| WO2015053339A1 (en) | 2015-04-16 |
| JP6358263B2 (en) | 2018-07-18 |
| JPWO2015053339A1 (en) | 2017-03-09 |
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