CN1292773A - Process for purifying perfluorocyclobutane - Google Patents

Process for purifying perfluorocyclobutane Download PDF

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CN1292773A
CN1292773A CN998036463A CN99803646A CN1292773A CN 1292773 A CN1292773 A CN 1292773A CN 998036463 A CN998036463 A CN 998036463A CN 99803646 A CN99803646 A CN 99803646A CN 1292773 A CN1292773 A CN 1292773A
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pfc
perfluorocyclobutane
hfc
pph
azeotrope
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CN1183072C (en
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C·P·C·考
B·A·马勒
R·N·米勒
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EIDP Inc
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EI Du Pont de Nemours and Co
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C23/00—Compounds containing at least one halogen atom bound to a ring other than a six-membered aromatic ring
    • C07C23/02—Monocyclic halogenated hydrocarbons
    • C07C23/06—Monocyclic halogenated hydrocarbons with a four-membered ring
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C19/00—Acyclic saturated compounds containing halogen atoms
    • C07C19/08—Acyclic saturated compounds containing halogen atoms containing fluorine
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C19/00—Acyclic saturated compounds containing halogen atoms
    • C07C19/08—Acyclic saturated compounds containing halogen atoms containing fluorine
    • C07C19/10—Acyclic saturated compounds containing halogen atoms containing fluorine and chlorine
    • C07C19/12—Acyclic saturated compounds containing halogen atoms containing fluorine and chlorine having two carbon atoms

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  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Disclosed is PFC-C318 containing less than 10 parts-per-million-molar of halogenated impurities and processes for producing such substantially-pure PFC-C318. In operating these processes, various PFC-C318-containing azeotropes and azeotrope-like compositions have been discovered and are of utility. These compositions comprise: perfluorocyclobutane (PFC-C318) and 2-chloro-1,1,1,2-tetrafluoroethane (HCFC-124); perfluorocyclobutane (PFC-C318) and 1,1,2,2-tetrafluoroethane (HFC-134); perfluorocyclobutane (PFC-C318) and 1,1,1,2-tetrafluoroethane (HFC-134a); and perfluorocyclobutane (PFC-C318) and 1,1-difluoroethane (HFC-152a). The processes of the present invention for producing substantially-pure PFC-C318 comprise: a) azeotropic distillation processes for separating PFC-C318 from halogenated impurities, and b) extractive distillation processes for separating PFC-C318 from halogenated impurities by employing entraining agents selected from ethers, ketones, alcohols, hydrocarbons, and hydrochlorocarbons.

Description

The method of purifying perfluorocyclobutane
The cross reference of related application
The application's book claims to the senior interest of No. the 60/076923rd, the U.S. Provisional Application of on March 5th, 1998 application.
Invention field
The present invention relates to contain the azeotropic and azeotrope-like (azeotrope-like) composition of perfluorocyclobutane and be used for isolating the component distillation of perfluorocyclobutane and the method for extractive distillation, thereby obtain highly purified perfluorocyclobutane with high-recovery from the original mixture that contains perfluorocyclobutane and halo impurity.
Background of invention
The gaseous state fluorochemicals is used for electronic industry and makes process for semiconductor devices.Perfluorocyclobutane in the manufacturing of semiconductor devices (PFC-C318) is mainly used in plasma etching (plasma etching) silicon section bar material.Plasma etchant such as PFC-C318 cracked (fragment) under plasma condition, the product that these are cracked and the surface interaction of semiconductor devices lay out circuit and the function of surface that is defined as integrated surface (surface functionalities) are provided thereby modify described surface.
The chemical substance such as the PFC-C318 that are used as plasma etchant in semiconductor fabrication applications are commonly referred to " electronic gas ".It is crucial having highly purified electronic gas in this application.Well-knownly be, both made very a spot of impurity also may produce wide line in the electronic gas, therefore, when this impure gas body was used to make the instrument of semiconductor devices, the information in each semiconductor devices was less.In addition, the existence of these impurity comprises particle, metal, moisture and halocarbon impurity, and the amount with ppm was existed, and also can increase the ratio of defects of making high density integrated circuit.The result is, electronic industry is growing to the demand of the etching gas of extreme high purity, and it is also growing to satisfy the marketable value of material of required purity.The identification of impurity and the method for removing them are importances of the etching gas used of preparation this respect.
The PFC-C318 of pure state has value in the manufacturing of unicircuit, and can be used for many manufacturing steps.In the manufacturing of unicircuit, need high precision more and stable effective electron gas (having) to make the gas of extreme high purity become these keys in using as PFC-C318.The halo impurity that exists among the PFC-C318 becomes this field and extends an obstacle of using.What need is the method that can make near the PFC-C318 of 99.999% (mole) purity, and the method for the PFC-C318 of at least 99.9999% (mole) purity preferably can be provided.
Disclosed as No. the 5129997th, United States Patent (USP), can be by pyrolysis chloro methylene fluoride (CHClF 2, HCFC-22) produce PFC-C318.Be difficult to from product stream, obtain the PFC-C318 of based on very high purity by this method, because also produce many halo impurity, they perhaps show imperfect behavior and make them approaching or even be 1.0 with the relative volatility of PFC-C318 separately the time or very approaching with the boiling point of PFC-C318 under the pure state.The relative volatility of those and PFC-C318 near or equal 1.0 impurity, make and can not by the routine distillation they and PFC-C318 be separated effectively when removing impurity and receive product P FC-C318 back and forth.When needs reclaim basic Halogen for the product P FC-C318 of impurity and when need be from the mixture that contains PFC-C318 and impurity reclaiming product P FC-C318 with high-recovery, this separation especially has problem.
Being used for the ordinary method of production product P FC-C318 can not produce and have 99.999% (mole) or more highly purified product P FC-C318, because they can not remove various halo impurity from product P FC-C318.Before the present invention, also do not heard and to have produced product P FC-C318 with 99.999% (mole) or higher mole percent purity.
The present invention solves and the relevant problem of conventional distillating method by providing distillating method to remove halo impurity from PFC-C318, thereby produces highly purified PFC-C318 with high-recovery.
Summary of the invention
The present invention comprises the PFC-C318 of basic Halogen for impurity, and preferred contained halo impurity is less than 10ppm (mole).
The present invention further comprises Azeotrope compositions, mainly is made up of following: perfluorocyclobutane (PFC-C318) and 2-chloro-1,1,1,2-Tetrafluoroethane (HCFC-124); Perfluorocyclobutane (PFC-C318) and 1,1,2,2-Tetrafluoroethane (HFC-134); Perfluorocyclobutane (PFC-C318) and 1,1,1,2-Tetrafluoroethane (HFC-134a); And perfluorocyclobutane (PFC-C318) and 1,1-C2H4F2 C2H4F2 (HFC-152a).The present invention also comprises azeotropic distn and extractive distillation method, is used for isolating perfluorocyclobutane (PFC-C318) from the initial mixture that contains perfluorocyclobutane (PFC-C318) and halo impurity.
The summary of figure
Fig. 1 diagram is used to implement the Distallation systm of an aspect of present method.
Fig. 2 is shown in azeotropic or the Azeotrope-like compositions of mainly being made up of PFC-C318 and HCFC-124 under 20 ℃ of temperature.
Fig. 3 is shown in azeotropic or the Azeotrope-like compositions of mainly being made up of PFC-C318 and HCFC-124a under 20 ℃ of temperature.
Fig. 4 is shown in 0 ℃ of azeotropic or Azeotrope-like compositions of mainly being made up of PFC-C318 and HFC-134 down.
Fig. 5 is shown in 0 ℃ of azeotropic or Azeotrope-like compositions of mainly being made up of PFC-C318 and HFC-134a down.
Fig. 6 is shown in 0 ℃ of azeotropic or Azeotrope-like compositions of mainly being made up of PFC-C318 and HFC-152a down.
Describe in detail
The present invention includes the PFC-C318 of substantially free of impurities. Impurity refers to be different from PFC-C318 Halogenated compound. Substantially do not have or the substantially pure PFC-C318 that refers to by the inventive method production Contain less than 10/1000000ths moles (ppmm), preferably less than 1ppmm, most preferably less than 10 The halo impurity of 100/100000000ths moles (ppbm). Therefore, the present invention includes and contain less than 10 Ppmm preferably less than 1ppmm, is more preferably less than the PFC-C318 of 100ppbm impurity. Operablely be used for that the analytical method of impurity concentration is disclosed among the assay products PFC-C318 " Examining Purification and Certification Strategies for High-Purity C2F 6Process Gas ", Micro Magazine, April 1998, and homepage is the 35th page, This introduces with for referencial use.
The method that is used for producing PFC-C318 can be produced each in the PFC-C318 product stream simultaneously Plant halo impurity. The example of the halo impurity of finding in the PFC-C318 product stream comprise straight chain and Ring-type, saturated and undersaturated perfluocarbon (PFCs), cfc (CFCs), hydrogen chlorofluorination Carbon (HCFCs), hydrofluorocarbons (HFCs) and hydrochlorinate carbon (HCCs). The generation of these halo impurity Table property example comprises: PFC-31-10 (just or different-C4F 10, the perfluorinated butane isomers), PFC-41-12 (C5F 12, the perflenapent isomers), PFC-1318my (cis or trans-CF3CF=CFCF 3)、PFC-1318c(CF 3CF 2CF=CF 2), PFC-1216 (HFP or CF3CF=CF 2), PFC-1114 (TFE or CF2=CF 2) perfluoroisobutylene (CF2=C(CF 3) 2)、 CFC-114(CF 2ClCF 2Cl)、CFC-114a(CFCl 2CF 3)、 CFC-216ba(CF 3CFClCF 2Cl)、CFC-217ba(CF 3CClFCF 3)、 CFC-1113(CClF=CF 2)、HCFC-22(CHClF 2)、HCFC-21(CHCl 2F)、 HCFC-124(CHFClCF 3)、HCFC-124a(CClF 2CHF 2)、HFC-134(CHF 2CHF 2)、 HFC-134a(CH 2FCF 3)、HFC-152a(CH 3CF 2H)、HFC-125(CF 3CF 2H)、 HFC-227ca(CF 3CF 2CHF 2)、HFC-227ea(CF 3CHFCF 3)、 HFC-1225zc(CF 3CH=CF 2)、HFC-236ca(CHF 2CF 2CHF 2)、 HFC-236ea(CHF 2CHFCF 3)、HFC-236fa(CF 3CH 2CF 3)、HCC-30(CH 2Cl 2)、 HCC-40(CH 3Cl) and HCC-160 (CH3CH 2Cl)。
Several and the PFC-C318 of these impurity forms azeotropic or azeotrope-like mixture, makes that obtain pure substantially PFC-C318 from this product stream becomes difficult high-recovery.The impurity that these and PFC-C318 form azeotropic or azeotrope-like mixture comprises HCFC-124, HCFC-124a, HFC-134, HFC-134a and HFC-152a.Other several halo impurity that produce during the HCFC-22 pyrolysis, bring obvious problem in the process that obtains substantially pure product P FC-C318 comprise PFC-1318my, PFC-31-10, PFC-1318c, CFC-114 and CFC-114a.
High-recovery is meant that the rate of recovery of PFC-C318 is preferably greater than 95% greater than 90% in the original mixture as the result of the method for purification of the product P FC-C318 that does not have at least a halo impurity substantially.
Azeotropic or Azeotrope-like compositions are meant the mixture of two or more compounds with constant boiling point, the similar a kind of purified compound of its behavior.The steam that a kind of method of identification Azeotrope compositions is produced by liquid portion evaporation or distillation has and is evaporated or distillating liquid is identical forms; Promptly form constant distillation/backflow mixture.Composition with constant boiling point is called azeotrope, at this moment compares with the zeotrope of same composition, and they have maximum or minimum boiling point.The feature of Azeotrope compositions is that also described mixture has minimum or top steam pressure with reference to the vapor pressure of pure component under steady temperature.
The azeotrope-like thing is meant to have the constant boiling point of characteristic or can not fractionated composition in boiling or when evaporation.Therefore, the composition of the steam of formation is formed identical or basic identical with original liquid.When boiling or evaporation, described liquid is formed, and has both made change, also just changes in minimum or insignificant scope.The feature of Azeotrope-like compositions is that also pressing adjacent area with maximum or minimum steam in giving the vapour pressure composition diagram of fixed temperature is the function of the molar fraction of described composition component.If a composition is the azeotrope-like thing, when boiling or evaporate the initial composition of about 50% (weight) and when obtaining remaining composition, the difference of initial composition and remaining composition is no more than about 6% (weight), compares with initial composition, is no more than about 3% (weight) usually.
The boiling point under this pressure is low separately than any compound of forming it for the boiling point that lower boiling azeotrope or Azeotrope compositions are meant composition under any setting pressure.Perhaps, lower boiling azeotrope or Azeotrope compositions are meant the vapour pressure of composition under any given temperature the pressure under this temperature are big separately than any compound of forming described azeotrope.
The boiling point that the high boiling point azeotrope is meant under any setting pressure azeotrope or Azeotrope-like compositions is than any compound of forming it boiling point height under this pressure separately.Perhaps, the high boiling point azeotrope is meant the vapour pressure of under any given temperature azeotrope or Azeotrope-like compositions the pressure under this temperature is little separately than any compound of forming described azeotrope.
Also azeotrope or Azeotrope-like compositions can be called the substantially invariable mixture of boiling point that can occur down in many illusions (guises).According to selected condition, following standard is arranged:
* this composition can be defined as the azeotrope of two kinds of compounds, because term " azeotrope " has determinacy and restricted at the very start, and requires this significant quantity with two or more compounds of the independent composition that constant boiling point forms.
What * be well known to those skilled in the art is, as boiling temperature, changes at least within the specific limits at the composition of next given azeotrope of different pressures or Azeotrope-like compositions.Therefore, the azeotrope of two kinds of compounds or Azeotrope-like compositions and variable composition have unique relation, and described variable composition depends on temperature and/or pressure.Therefore, the scope of composition, rather than fixing the composition are used to define azeotrope and Azeotrope-like compositions usually.
* the azeotrope of two kinds of compounds or Azeotrope-like compositions are characterised in that by the boiling point under a setting pressure and come the definitions section compound, therefore form to provide by the numeral of determining and be not to be used for excessively limiting the recognition feature of the scope of the invention, it is subjected to the restriction of existing analytical instrument but is unique accurate.
In the art, well-known is when described liquid Azeotrope compositions seethes with excitement under different pressures, and the amount of every kind of component all may change in boiling point and the described composition.Therefore, can according to be present in the component unique relationships or according to have one determine under the pressure corresponding one fixedly in the composition of boiling point the set amount of every kind of component define a kind of Azeotrope compositions.
It is well known in the art that relative volatility when an individual system, for example, the mixture that contains PFC-C318 and halo impurity of the present invention, near 1.0 o'clock, can define described system was Azeotrope-like compositions.When relative volatility equals 1.0, can define described system is Azeotrope compositions.The relative volatility of those and PFC-C318 near or equal 1.0 impurity extremely difficulty maybe can not separate from PFC-C318 by the routine distillation.Conventional distillation is meant that the relative volatility of only utilizing component of mixture to be separated separates these components.
For calculating the relative volatility of any two kinds of components, can adopt the method that is called PTx.In this method, measure one oneself know the different absolute stagnation pressures of forming of two kinds of compounds of the steady temperature in the pond of volume.The use of PTx method is described in detail referring to " balancing each other in the process design ", Wiley-Interscience Publisher, 1970, Harold R.Null work, 124-126 page or leaf; Be incorporated herein by reference.
By using the activity coefficient equation model, as Non-Random, Two-Liquid (NRTL) equation, the steam and the liquid that these observed values can be converted into equilibrium state in the PTx pond (cell) are formed the imperfect attitude of representing liquid phase.The application of activity coefficient equation,, the 4th edition, publish referring to " character of gas and liquid " as the equational detailed description of NTRL by McGraw Hill, Reid, Prausnitz and Poling work, 241-387 page or leaf, and " balancing each other in the chemical engineering ", publish by Butterworth Publishers, 1985, Stanley M.Walas work, 165-244 page or leaf.Two references in front are hereby incorporated by.
Be reluctant to be subjected to the constraint of any theory or explanation, can think that the NRTL equation is with PTx pond data, be enough to predict the relative volatility of PFC-C318 of the present invention, halo impurity and entrainment agent (entrainingagents), and therefore can predict the behavior of these mixtures in stage trapping equipment such as distillation tower.
Surprisingly, the inventor finds that PFC-C318 and HCFC-124 are at 20 ℃ and 49psia (pound/per square inch, can form the Azeotrope compositions of the HCFC-124 of the PFC-C318 and 73.2% (mole) that contains 26.8% (mole) definitely) down.Can calculate under 0 ℃ and 24.6psia the HCFC-124 of the PFC-C318 and 73.2% (mole) that azeotrope that is formed by PFC-C318 and HCFC-124 or Azeotrope-like compositions contain 26.8% (mole) from these data.Can calculate under 80 ℃ and 234.1psia the HCFC-124 of the PFC-C318 and 72.5% (mole) that azeotrope that is formed by PFC-C318 and HCFC-124 or Azeotrope-like compositions contain 27.5% (mole) from these data.Correspondingly, the present invention further comprises azeotrope or the Azeotrope-like compositions of the HCFC-124 of the PFC-C318 that contains 26.8-27.5% (mole) and 73.2-72.5% (mole), and the boiling point of described composition is under the 24.5psia 0 ℃ under the 234.1psia 80 ℃.
Surprisingly, the inventor finds that PFC-C318 and HFC-134 form the HFC-134 Azeotrope compositions of the PFC-C318 and 75.0% (mole) that contains 25.0% (mole) under 0 ℃ and 36.4psia.Can calculate under-30.0 ℃ and 10.35psia the HFC-134 of the PFC-C318 and 75.4% (mole) that azeotrope that is formed by PFC-C318 and HFC-134 or Azeotrope-like compositions contain 24.6% (mole) by these data.Can calculate under 80 ℃ and 325.8psia the HFC-134 of the PFC-C318 and 76.8% (mole) that azeotrope that is formed by PFC-C318 and HFC-134 or Azeotrope-like compositions contain 23.2% (mole) by these data.Correspondingly, the present invention further comprises azeotrope or the Azeotrope-like compositions of the HFC-134 of the PFC-C318 that contains 24.6-23.2% (mole) and 75.4-76.8% (mole), and the boiling point of described composition is-30 ℃ of under the 325.8psia 80 ℃ under the 10.35psia.
Surprisingly, the inventor finds that under 0 ℃ and 43psia PFC-C318 and HFC-134a form the HFC-134a of the PFC-C318 and 92.6% (mole) that contains 7.4% (mole).Can calculate under-30 ℃ and 12psia the HFC-134a of the PFC-C318 and 90.1% (mole) that azeotrope that is formed by PFC-C318 and HFC-134a or Azeotrope-like compositions contain 9.9% (mole) by these data.Can calculate under 40 ℃ and 147psia the HFC-134a of the PFC-C318 and 99.4% (mole) that azeotrope that is formed by PFC-C318 and HFC-134a or Azeotrope-like compositions contain 0.6% (mole) by these data.Correspondingly, the present invention further comprises azeotrope or the Azeotrope-like compositions of the HFC-134a of the PFC-C318 that contains 9.9-0.6% (mole) and 90.1-99.4% (mole), and the boiling point of described composition is-30 ℃ of under the 147psia 40 ℃ under the 12psia.
Surprisingly, the inventor finds that PFC-C318 and HFC-152a form the HFC-152a of the PFC-C318 and 76.9% (mole) that contains 23.1% (mole) under 0 ℃ and 41psia.Can calculate under-20 ℃ and 19psia the HFC-152a of the PFC-C318 and 77.6% (mole) that azeotrope that is formed by PFC-C318 and HFC-152a or Azeotrope-like compositions contain 22.4% (mole) by these data.Can calculate under 80 ℃ and 349psia the HFC-152a of the PFC-C318 and 78.7% (mole) that azeotrope that is formed by PFC-C318 and HFC-152a or Azeotrope-like compositions contain 21.3% (mole) by these data.Correspondingly, the present invention further comprises azeotrope or the Azeotrope-like compositions of the HFC-152a of the PFC-C318 that contains 23.1-21.3% (mole) and 76.9-78.7% (mole), and the boiling point of described composition is-20 ℃ of under the 349psia 80 ℃ under the 19psia.
In another aspect of this invention, under this condition, thereby distillation contains the lower boiling azeotrope that the mixture of PFC-C318 and at least a this type of halo impurity forms described PFC-C318 of containing and described impurity, and with the distillation in product of distillation remove described azeotrope and Azeotrope-like compositions, PFC-C318 is separated to a certain extent with described impurity.Component distillation is meant a kind of method, forms azeotrope or Azeotrope-like compositions thereby wherein operate distillation tower under certain condition, thereby this formation changed the relative volatility of at least one component and another component, thereby can pass through these components of fractionation by distillation.
For example, contain the mixture of PFC-C318 and HCFC-124 by using aforesaid Azeotrope compositions partly to purify.The operation distillation tower forms the lower boiling azeotrope that contains PFC-C318 and HCFC-124 under certain pressure and temperature, and removes described azeotrope with the form of top stream from distillation tower.If the concentration of PFC-C318 is greater than the concentration in the PFC-C318/HCFC-124 azeotrope that forms under distillation condition in the original mixture (PFC-C318/HCFC-124 mixture material to be separated), can when the distillation original mixture, remove product P FC-C318 with the form of bottom stream, wherein compare with original mixture, the concentration of HCFC-124 diminishes in the bottom stream, simultaneously, the PFC-C318/HCFC-124 azeotrope is removed from distillation tower with the form of top stream.On the contrary, if the concentration of HCFC-124 is greater than the concentration in the Azeotrope compositions that contains PFC-C318/HCFC-124 that forms under distillation condition in the original mixture, can when the distillation original mixture, remove product HCFC-124 with the form of bottom stream, compare with original mixture, the concentration of PFC-C318 diminishes in the bottom stream, simultaneously, the PFC-C318/HCFC-124 azeotrope is removed from distillation tower with the form of top stream.Obtain PFC-C318 by single flash, compare with initial PFC-C318/HCFC-124 mixture, wherein the concentration of HCFC-124 diminishes and (or obtains HCFC-124, compare with initial PFC-C318/HCFC-124 mixture, wherein the concentration of PFC-C318 diminishes), this single flash requires the concentration of PFC-C318 (or HCFC-124) in the initial composition greater than the concentration in the Azeotrope compositions that forms under uniform temp and the pressure.But must still have a certain proportion of PFC-C318 (or HCFC-124) to remain with the form of PFC-C318/HCFC-124 azeotrope.
When adopt to form and distill various PFC-C318 azeotropes (as PFC-C318/HCFC-124, PFC-C318/HFC-134, PFC-C318/HCFC-124a, PFC-C318/HFC-134a, PFC-C318/HFC-152a) and come when halo impurity separates PFC-C318, the Azeotrope compositions that contains PFC-C318 that obtains can be used as the feed fluid of thermal process (thermal process) production TFE and HFP.Perhaps, the PFC-C318 in the product of distillation can be come out for the isolated in form of impurity with basic Halogen by extractive distillation method of the present invention.
Then, although in distillation, use described Azeotrope compositions to help part purification PFC-C318 or halo impurity, be difficult to from the mixture of initial p FC-C318/ halo impurity, obtain pure substantially product P FC-C318 with high-recovery by component distillation.In addition, this component distillation often can not be removed other impurity that can not form Azeotrope compositions with PFC-C318.
Discovery prepares the relative volatility of many other halo impurity in the fluid near 1.0 (with respect to PFC-C318) at PFC-C318.These halo impurity comprise CFC-12, HCC-20, HCFC-22, HFC-32, CFC-114, CFC-114a, CFC-217ba, HFC-227ea, PFC-1318my, PFC-1318c and FC-31-10.CFC-114, CFC-114a, PFC-1318my, FC31-10 especially have problem, because their concentration is ppm hundred or several thousand (mole) or higher in PFC-C318 process fluid subsequently.Isolating these impurity from PFC-C318 needs high and expensive distillation tower, and if can not from these mixtures, obtain pure substantially PFC-C318 with high-recovery, this separation is still extremely difficult.
Unexpectedly, the inventor finds by using the compound of significant quantity, they are with at least a component effect in imperfect behavior and the initial PFC-C318/ halo mixtures of impurities, thereby can reclaim the PFC-C318 that does not contain these and other halo impurity substantially.These compounds, after this be called entrainment agent, compare with at least a halo impurity in the original mixture, under distillation condition, increase or reduce the volatility of PFC-C318, thereby can from the initial mixture that contains PFC-C318 and halo impurity, obtain the PFC-C318 of basic Halogen for impurity.
Therefore, the present invention also comprises the method that is used for separating PFC-C318 from least a halo impurity, and described method is included under the existence of at least a entrainment agent, and extractive distillation contains the mixture of PFC-C318 and halo impurity.Described method also comprises a kind of distillation, wherein in the presence of entrainment agent, compares with another for one, and the volatility of PFC-C318 or halo impurity increases.
Entrainment agent is meant any compound, when it joins the original mixture that contains PFC-C318 and halo impurity, with at least a PFC-C318 and the effect of halo impurity, thereby change in these components the volatility of other component in a kind of described relatively mixture, PFC-C318 can be separated by distillation with halo impurity like this.
The significant quantity of entrainment agent is meant the consumption of at least a entrainment agent, in the presence of PFC-C318 and halo impurity, makes the volatility of halo impurity, compares with PFC-C318, isolates halo impurity thereby fully increase or reduce by distillation from PFC-C318.This definition comprises such example, and according to the variation of the pressure that is applied to described composition, as long as the variation of relative volatility still exists, described significant quantity can change.
Extractive distillation is meant a kind of method, wherein imports from same feed point in view of described mixture to be separated, or preferably imports than importing the relatively low feed point of entrainment agent from described tower, and entrainment agent imports from the top charging opening of distillation tower.Described entrainment agent by described tower tower tray or packing layer and discharge with the form of bottom stream with one or more components of described mixture to be separated.In the presence of entrainment agent, to compare with at least a other component in the described mixture, at least a relative volatility becomes big or diminishes in the component to be separated, and volatile components leaves with the form of distillation overhead streams.Entrainment agent adds distillation tower and is downward through described tower from the point that is equal to or higher than mixture to be separated, can separate by distillation like this.Described entrainment agent is called extractive distillation agent or extraction agent herein.
Be further this extractive distillation of definition method, the inventor oneself through find in the extractive distillation process can be by using entrainment agent will be present among the PFC-C318 among halo impurity F C-31-10, FC-1318my, FC-1318c, HFC-134, HFC-134a, HCFC-124, HCFC-124a, CFC-114, CFC-114a, CFC-217ba, the HCC-20 any and other optional halogenated compound is separated from described PFC-C318.Can comprise as the suitable entrainment agent that from these halo impurity, separates the extraction agent of PFC-C318: ethers, ketone, alcohols, hydro carbons and hydrochlorinate carbon.Can it be 30-120 ℃ as the entrainment agent preferred standard boiling point that is suitable for of extraction agent in the present invention.The ether that is suitable for comprises tetrahydrofuran (THF) (THF), 1,4-diox and dialkyl ether such as methyl tertiary butyl ether (MTBE).The ketone that is suitable for comprises acetone, methylethylketone (MEK).The alcohol that is suitable for comprises methyl alcohol and propyl alcohol.The hydrocarbon that is suitable for comprises toluene and hexanaphthene, and suitable hydrochlorinate carbon comprises chloroform (CH 3Cl).Is THF, MEK and 1 by extractive distillation from the preferred entrainment agent that PFC-C318 separates halo impurity, the 4-diox.
In the presence of no described extraction agent, with reference to the relative volatility of described halo impurity, so that halo impurity is difficult to separate from PFC-C318 by the routine distillation to PFC-C318.In the presence of at least a described extraction agent, contrast aforesaid halo impurity, the volatility of PFC-C318 changes astoundingly.Therefore, in the presence of at least a described extraction agent, PFC-C318 can separate and do not had substantially the product of described halo impurity by extractive distillation from described halo impurity.The present invention also provides a kind of method, shifts out PFC-C318 from described halo impurity, thereby with the described halo impurity of the streamed recovery of the product that does not have PFC-C318 substantially.
Except some halo impurity such as FC-31-10, in the presence of extraction agent of the present invention, halo impurity is unexpectedly than the difficult volatilization of PFC-C318.In the presence of extraction agent, like this can the extractive distillation cat head form of stream obtain the PFC-C318 of basic Halogen for impurity, and reclaim halo impurity and extraction agent with the form of base product effluent.
The present invention further comprises a kind of method that is used for separating PFC-C318 and at least a described halo impurity like this, comprise: form second mixture thereby a) original mixture that contains PFC-C318 and at least a halo impurity is contacted with entrainment agent, and b) distill second mixture and reclaim distillation overhead streams that contains PFC-C318 and the base product effluent that contains entrainment agent and at least a halo impurity.
Compare with other aforementioned halo impurity, PFC-31-10, normal boiling point is greater than PFC-C318, it is more volatile than PFC-C318 to become astoundingly in the presence of this extraction agent, like this PFC-31-10 can the extractive distillation cat head form of stream separate from PFC-C318, and do not had the PFC-C318 of PFC-31-10 substantially with the form of extraction bottom stream.
The present invention further comprises a kind of method that is used for separating PFC-C318 and PFC-31-10 like this, comprise: the original mixture that contains PFC-C318 and PFC-31-10 is contacted with entrainment agent, thereby form second mixture, and b) distillation second mixture and recovery contain the distillation overhead streams of PFC-31-10 and contain entrainment agent and the base product effluent of PFC-C318.
Fig. 1 graphic extension can be used for implementing a system of this extractive distillation method part.The original mixture that contains PFC-C318 and PFC-31-10 adds distillation tower 2 by conduit 1.With at least a entrainment agent, as THF, add distillation tower 2 by conduit 3, its feed point is higher than the feed point of mixture to be separated such as PFC-C318 and PFC-31-10.To add condenser 5 by conduit 4 from the top distillate of described distillation tower.At least the overhead product of partial condensation returns tower 2 with reflux type 6.The overhead product of remaining condensation is reclaimed by the form of conduit 7 with the product P FC-31-10 that do not have PFC-C318 and THF substantially.To contain fluid PFC-C318 and THF, that do not have a PFC-31-10 substantially shifts out and reclaims as product from tower 2 bottoms by conduit 8.Perhaps, described bottom stream 8 is added distillation tower 9, operate described distillation tower 9, stripping compound from entrainment agent.To add condenser 11 by conduit 10 from the overhead product of tower 9.The distillate of a certain amount of condensation returns tower 9 in the mode that refluxes by conduit 12 from condenser 11, and described residuum is with the product form, as reclaiming by conduit 13 with the form of not having the PFC-31-10 and the PFC-C318 of extraction entrainment agent substantially.Compare with the concentration of non-THF in the stream 8,, obtain extracting entrainment agent with the form of base product effluent 14, as THF along with the reduction of non-THF compound concentration.Stream 14 can be chosen wantonly to extract reinforced mode and returns distillation tower 2, and the feed point that enters described tower is higher than the feed point of mixture to be separated such as PFC-31-10 and PFC-C318, maybe can choose wantonly and flows 3 and mix.
Fig. 1 can also be used for system of graphic extension, and described system can be used to implement another embodiment of extractive distillation method of the present invention.The original mixture that will contain PFC-C318 and FC-1318my adds distillation tower 2 by conduit 1.With at least a extraction entrainment agent, as THF, add distillation tower 2 by conduit 3, its feed point is higher than the feed point of mixture to be separated such as PFC-C318 and FC-1318my.To send into condenser 5 by conduit 4 from the top distillate of described tower.At least the distillate of partial condensation stream returns tower 2 with reflux type.The overhead product of remaining condensation is reclaimed by the form of conduit 7 with the product P FC-C318 that do not have FC-1318my and THF substantially.To contain stream FC-1318my and THF, that do not have a PFC-C318 substantially shifts out from tower 2 bottoms by conduit 8.Perhaps, described bottom stream 8 is added distillation tower 9, operate the non-entrainment agent compound of described distillation tower 9 stripping from entrainment agent.To add condenser 11 by conduit 10 from the distillate of tower 9.The distillate of a certain amount of condensation returns tower 9 in the mode that refluxes by conduit 12 from condenser 11, and described residuum is with the product form, as reclaiming by conduit 13 with the form of not having the PFC-C318 and the FC-1318my of extraction entrainment agent substantially.Compare with the concentration of non-THF in the stream 8,, obtain extracting entrainment agent with the form of base product effluent 14, as THF along with the reduction of non-THF compound concentration.Stream 14 can be chosen wantonly in the reinforced mode of extraction agent and return distillation tower 2, and the feed point that enters described tower is higher than the feed point of mixture to be separated such as PFC-C318 and FC-1318my, maybe can choose wantonly and flows 3 and mix.
Usually, component distillation or extractive distillation are left the top stream of described tower or are distillated liquid and can use the normal reflux condenser to carry out condensation.At least a portion of this condensate flow can be returned cat head by reflux type, and residuum is with the form of product or be used for other processing and reclaim.The condensed material of returning cat head with reflux type is called reflux ratio with the ratio of the material that shifts out.In the example that uses entrainment agent, to leave the compound and the entrainment agent of described tower with the form of bottom stream subsequently, by adopting conventional distillation or other own perception method, separate through a stripper or other distillation tower, and, if desired, entrainment agent is recycled to first distillation tower.
The actual conditions that can be used for implementing present method depends on many parameters, as the separation progression of the diameter of distillation tower, feed point, tower and other.The working pressure of Distallation systm can be 15-500psia, is generally 50-400psia.Typically, with reference to the feed rate of mixture to be separated, the feed rate that increases entrainment agent is improved degree of purity of production to be recycled (with reference to those components that are moved out of).Increase reflux ratio, cause the reducing of concentration of extraction agent in the distillate stream usually.But reflux ratio is 1/1-200/1 usually.Usually should be enough to make the basic total condensation of the distillate that leaves cat head with the temperature of the condenser of described top of tower adjacency, perhaps, require temperature to obtain the reflux ratio of required partial condensation.
Be applicable to that the present invention purifies, as to contain PFC-C318 mixture can be obtained by any preparation method or the source that produce or produce the mixture that contains PFC-C318.For example, can produce PFC-C318 by pyrolysis HCFC-22.Perhaps, the mixture that contains PFC-C318 can and need be obtained by the preparation method that described method reclaims described PFC-C318 by any use PFC-C318.If desired, can use conventional distillation to reduce the original bulk of halo impurity.That is to say that can use conventional distillation to remove many relatively or a large amount of halo impurity from the mixture that contains PFC-C318, described subsequently mixture reclaims and purification PFC-C318 according to the inventive method.
Embodiment
The all respects that provide following embodiment that the inventive method is described are not used for limiting the scope of the invention.Following embodiment adopts the NRTL interaction parameter of early determining.In the following embodiments, every grade is benchmark with 100% operation or operational efficiency.When using different extraction agent, adopt different tower designs and operational condition and make each distillatory operation maximization.In all embodiments, total progression comprises condenser and reboiler, together with condenser as the first step.In all embodiments, the flow of stream is in pound (pph) per hour, or represents in mole number (mph) per hour; Temperature (" TEMP ") with degree centigrade (℃) represent; Concentration is with molar percentage (mole%), weight percent (wt%), mole 1,000,000 umbers (ppm-molar) and weight 1,000,000 umbers (ppm-wt) expression; Remove or put into the heat flow rate (" DUTIES ") of the reboiler of distillation tower represents with pcu/hour or pcu/hr from condenser; Pressure (" PRES ") usefulness poundage (absolute pressure) per square inch (psia) is represented.Various values are used to represent base product effluent (" BTMS "), distillate (" DIST "), condenser (" CONDSR "), reflux (" REFLUX ") and top stream (" TOP ").Value also represents to be used for the stream (" FEED ") of isolating adding tower and the extraction agent of any adding tower (" EXTR " or " EXTR FEED ").In these embodiments, the rate of recovery (" RECOV.EFF. ") is meant the percentage that adds described distillatory C318, and described distillation is used for reclaiming C318 product stream.
Comparative example 1.2.3
In comparative example 3, will contain the PFC-C318 of 980pph and the C of 20pph at comparative example 1 4F 10(PFC-31-10) mixture adds distillation tower, uses conventional the distillation subsequently under certain condition, thereby shifts out that the PFC-C318 product flows and shift out C with the form of bottom stream with the form of distillate 4F 10Product stream.Described distillatory actual conditions and the results are shown in table 1.
1 1 2 3 114 228 144 58 114 72REFLUX TEMP ( ℃ ) 7．3 7．3 7．3DIST TEMP ( ℃ ) 7．3 7．3 7．3BTMS TEMP ( ℃ ) 10．7 10．7 13．5FEED TEMP ( ℃ ) 10．5 10．5 10．5TOP PRES ( PSIA ) 24．7 24．7 24．7CONDSR PRES ( PSIA ) 24．7 24．7 24．7BTMS PRES ( PSIA ) 27．7 27．7 24．7 ( PPH ) 800．0 800．0 975．0 ( PPH ) 13888．0 28551．0 160531．0 ( PPH ) 200．0 200．0 25．0 ( PCU／HR ) -385645．-770645．-4240779． ( PCU／HR ) +385000． +770000． +4240000． PFC-C318 ( PPH ) 980． 980． 980． C4F 10(PPH) 20. 20. 20. form C 4F 10(PPM-weight) 20000. 20000. 20000. C 4F 10(PPM-mole) 16861. 16861. 16861. tower distillate flow PFC-C318 (PPH) 799.40 800.0 975.0 C 4F 10(PPH) 0.60 0.00 0.0073 forms C 4F 10(PPM-weight) 754. 4.1 7.5 C 4F 10(PPM-mole) 634. 3.4 6.3PFC-C318 RECOV.EFF. (%) 81.57 81.63 99.49 bottom stream flow PFC-C318 (PPH) 180.6 180.0 5.0 C 4F 10(PPH) 19.40 20.00 19.99
In comparative example 1, contain the C of 634ppmm from this conventional distillatory PFC-C318 product fluid 4F 10And the rate of recovery of PFC-C318 only about 82%.
Comparative example 2 is compared with comparative example 1, and the heat load of the sum of series reboiler of tower all increases and is twice.However, the product P FC-C318 that obtains still contains the C greater than 3ppmm 4F 10And the rate of recovery of PFC-C318 only about 82%.
Comparative example 3 is compared with comparative example 1, and the distillatory reflux rate has increased about 10 times, is reduced to about 1/10th of comparative example 1 and the PFC-C318 tower bottom flow goes out speed.Although the rate of recovery is increased to 99.0%, PFC-C318 product fluid still contains the C of 6.3ppmm 4F 10
These comparative example explanations are difficult to from containing PFC-C318 and C by the routine distillation 4F 10Initial flow in obtain the pure substantially PFC-C318 product stream of high-recovery.
Comparative example 4,5
In comparative example 4 and 5, will add distillation tower as the listed mixture that contains PFC-C318 and impurity of table 2.Use conventional distillation that described mixture is distilled under certain condition, thereby shift out the product stream that contains PFC-C318 from described tower, and shift out the product stream that contains impurity with the form of bottom stream with the form of distillate.Described distillatory actual conditions and the results are shown in table 2.
2 4 5 114 228 58 114TOP TEMP ( ℃ ) 7．3 7．3REFLUX TEMP ( ℃ ) 7．3 7．3DIST TEMP ( ℃ ) 7．3 7．3BTMS TEMP ( ℃ ) 10．5 10．5FEED TEMP ( ℃ ) 10．5 10．5TOP PRES ( PSIA ) 24．7 24．7CONDER PRES ( PSIA ) 24．7 24．7BTMS PRES ( PSIA ) 27．7 27．7 ( PPH ) 800．0 800．0 ( PPH ) 20360． 41118． ( PPH ) 200． 200． ( PCU／HR ) -555645．-1100645． ( PCU／HR ) +555000． +1100000． PFC-C318 ( PPH ) 998．9 998．9 CFC-114 ( PPH ) 1．0 1．0 HFC-124a ( PPH ) 0．200E-01 0．200E-01 CFC-217ba ( PPH ) 0．10 0．10 PFC-1318my ( PPH ) 0．200E-01 0．200E-01 ( PPM- ) 1140．0 1140．0 ( PPM- ) 1317．2 1317．2 PFC-C318 ( PPH ) 799．9 800．0 CFC-114 ( PPH ) 0．345E-01 0．440E-03 HFC-124a ( PPH ) 0．200E-01 0．200E-01 CFC-217ba ( PPH ) 0．552E-02 0．117E-03 PFC-1318my ( PPH ) 0．139E-05 0．439E-10 CFC-114 ( PPM- ) 50．4 0．64 HFC-124a ( PPM- ) 36．6 36．6 CFC-217ba ( PPM- ) 6．7 0．14 PFC-1318my ( PPM- ) 0．0017 0．548E-07 ( PPM- ) 93．8 37．4 PFC-C318 ( ％ ) 99．992503 99．997430 PFC-C318 ( ％ ) 99．990620 99．996257 PFC-C318 RECOV．EFF． ( ％ ) 80．09 80．09 PFC-C318 ( PPH ) 198．9 198．9 CFC-114 ( PPH ) 0．97 1．00 HCFC-124a ( PPH ) 0．105E-17 0．467E-33 CFC-217ba ( PPH ) 0．09 0．10 PFC-1318my ( PPH ) 0．200E-01 0．200E-01
Under the distillation condition of comparative example 4, reclaim PFC-C318 with distillate product form, the rate of recovery only is 80%, and total impurities content still has 94ppmm.
Comparative example 5 is compared with comparative example 4, and the sum of series reflux rate of tower all increases and is twice.However, the rate of recovery of PFC-C318 still only be 80% and the total impurities amount still have 37ppmm.
These comparative examples show, are difficult to flow with the pure substantially PFC-C318 product that the initial flow that is common in many impurity of PFC-C318 process flow obtains high-recovery from containing PFC-C318 by the routine distillation.Comparative example 6,7,8,9
At comparative example 6,7, in 8 and 9, the stream that will contain the HFC-134 of the PFC-C318 of 394pph and 606pph adds distillation tower.Distillation condition and the results are shown in table 3.
3 6 7 8 9 62 62 62 62 30 30 30 30TOP TEMP ( C ) -10．1-10．1-10．1-10．1REFLUX TEMP ( C ) -10．2-10．2-10．2-10．2DIST TEMP ( C ) -10．2-10．2-10．2-10．2BTMS TEMP ( C ) -7．3-7．3-7．3-7．3FEED TEMP ( C ) -7．3-7．3-7．3-7．3TOP PRES ( PSIA ) 24．7 24．7 24．7 24．7CONDSR PRES ( PSIA ) 24．7 24．7 24．7 24．7BTMS PRES ( PSIA ) 27．7 27．7 27．7 27．7 ( PPH ) 100．0 900．0 100．0 900．0 ( PPH ) 2000． 2000． 20000． 20000． ( PPH ) 900． 100． 900． 100． ( PCU／HR ) -89975．-124251．-861187．-895463． ( PCU／HR ) +89896． +123544． +861108． +894755． PFC-C318 ( PPH ) 394．0 394．0 394．0 394．0 HFC-134 ( PPH ) 606．0 606．0 606．0 606．0 PFC-C318 ( ％ ) 39．4 39．4 39．4 39．4 PFC-C318 ( ％ ) 24．9 24．9 24．9 24．9 PFC-C318 ( PPH ) 39．4 354．7 39．4 354．7 HFC-134 ( PPH ) 60．6 545．3 60．6 545．3 PFC-C318 ( ％ ) 39．4 39．4 39．4 39．4 PFC-C318 ( ％ ) 24．9 24．9 24．9 24．9 PFC-C318 ( PPH ) 354．6 39．3 354．6 39．3 HFC-134 ( PPH ) 545．4 60．7 545．4 60．7 PFC-C318 ( ％ ) 39．4 39．3 39．4 39．3 PFC-C318 ( ％ ) 24．9 24．9 24．9 24．9
By these comparative examples as can be seen, this distillatory result can not isolate PFC-C318 substantially from HFC-134, even change distillation rate on a large scale, tower bottom flow goes out speed and reflux rate.This is because PFC-C318 and HFC-134 are included in the Azeotrope compositions that is formed by PFC-C318 and HFC-134 under the operational condition of described tower toward the adding speed of distillation tower.This comparative example shows that can utilize routine to distill separates the Azeotrope compositions that contains PFC-C318 and HFC-134.
Comparative example 10,11,12,13
At comparative example 10,11, in 12,13, the mixture that will contain PFC-C318 and HFC-134 adds distillation tower.These distillatory conditions and the results are shown in table 4.
4 10 11 12 13 32 32 32 32 12 12 12 12TOP TEMP ( ℃ ) 1．4-1．3-10．0-10．1REFLUX TEMP ( ℃ ) -5．6-7．7-10．2-10．2DIST TEMP ( ℃ ) -5．6-7．7-10．2-10．2BTMS TEMP ( ℃ ) 10．5 10．5 10．5 10．5FEED TEMP ( ℃ ) 3．7 3．7 3．7 3．7TOP PRES ( PSIA ) 24．8 24．8 24．8 24．8CONDSR PRES ( PSIA ) 24．7 24．7 24．7 24．7BTMS PRES ( PSIA ) 27．7 27．7 27．7 27．7 ( PPH ) 338．8 226．5 86．7 82．5 ( PPH ) 150． 300． 400． 500． ( PPH ) 661． 774． 913． 917． ( PCU／HR ) -15741．-17960．-20505．-24961． ( PCU／H ) +16067． +18619．+21747． +26225． PFC-C318 ( PPH ) 950． 950． 950． 950． HFC-134 ( PPH ) 50． 50． 50． 50． HFC-134 ( PPM- ) 50000． 50000． 50000． 50000． HFC-134 ( PPM- ) 93532． 93532． 93532． 93532． PFC-C318 ( PPH ) 288．8 176．5 36．7 32．5 HFC-134 ( PPH ) 50．0 50．0 50．0 50．0 PFC-C318 ( ％ ) 85．2 77．9 42．3 39．4 PFC-C318 ( ％ ) 74．7 64．3 27．2 24．9 PFC-C318 ( PPH ) 661．2 773．5 913．3 917．5 HFC-134 ( PPH ) 0．00003 0．00004 0．00005 0．00005 HFC-134 ( PPM- ) 0．1 0．1 0．1 0．1 PFC-C318 ( ％ ) 99．99999 99．99999 99．99999 99．99999 PFC-C318 ( ％ ) 99．99999 99．99999 99．99999 99．99999 PFC-C318 RECOV．EFF． ( ％ ) 69．6 81．4 96．1 96．6
In these embodiments, operate described distillation tower under certain condition and form the PFC-C318/HFC-134 Azeotrope compositions, wherein the concentration of PFC-C318 is less than the concentration of the mixture that adds.Lower boiling PFC-C318/HFC-134 azeotrope becomes the cat head effluent and the PFC-C318 that surpasses described Azeotrope compositions amount that adds obtains reclaiming in bottom stream.
Along with the increase of reflux rate, the efficient from Azeotrope compositions excessive separation PFC-C318 in distillation tower increases in comparative example 10,11,12 and 13, and form that like this can bottom stream reclaims this excessive PFC-C318 that does not have HFC-134 substantially.Yet the increase of this effect requires to enlarge markedly reflux rate, and significantly reduces the speed of the distillate product that obtains.In addition, the PFC-C318 of some addings must be retained in a part that becomes the PFC-C318/HFC-134 Azeotrope compositions in the distillate, has limited the possible rate of recovery (by this component distillation) of PFC-C318.
Yet, these comparative examples show that the lower boiling Azeotrope compositions that how will contain PFC-C318 and HFC-134 is used for shifting out HFC-134 from the original mixture that contains PFC-C318 and HFC-134, can not had the PFC-C318 product fluid of HFC-134 so substantially.
Comparative example 14,15,16,17
In comparative example 14,15,16,17, the mixture that will contain PFC-C318 and HFC-134 adds distillation tower.These distillatory conditions and the results are shown in table 5.
5 14 15 16 17 62 62 62 62 30 30 30 30TOP TEMP ( ℃ ) -8．3-9．3-10．1-10．1REFLUX TEMP ( ℃ ) -9．1-9．9-10．2-10．2DIST TEMP ( ℃ ) -9．1-9．9-10．2-10．2BTMS TEMP ( ℃ ) -4．3-4．3-4．3-4．3FEED TEMP ( ℃ ) -5．2-5．2-5．2-5．2TOP PRES ( PSIA ) 24．7 24．7 24．7 24．7CONDSR PRES ( PSIA ) 24．7 24．7 24．7 24．7BTMS PRES ( PSIA ) 27．7 27．7 27．7 27．7 ( PPH ) 389．2 206．9 126．9 126．9 ( PPH ) 500． 1000． 1500． 2000． ( PPH ) 611． 793． 873． 873． ( PCU／HR ) -44097．-56438．-69704．-91127． ( PCU／HR ) +43827． +56376． 69760． 91182． PFC-C318 ( PPH ) 50． 50． 50． 50． HFC-134 ( PPH ) 950． 950． 950． 950． PFC-C318 ( PPM- ) 50000． 50000． 50000． 50000． PFC-C318 ( PPM- ) 26144． 26144． 26144． 26144． PFC-C318 ( PPH ) 50．0 50．0 50．0 50．0 HFC-134 ( PPH ) 339．2 156．9 76．9 76．9 PFC-C318 ( ％ ) 12．8 24．2 39．4 39．4 PFC-C318 ( ％ ) 7．0 14．0 24．9 24．9 PFC-C318 ( PPH ) 0．00012 0．00016 0．00017 0．00017 HFC-134 ( PPH ) 610．8 793．1 873．1 873．1 PFC-C318 ( PPM- ) 0．1 0．1 0．1 0．1 HFC-134 ( ％ ) 99．99998 99．99998 99．99998 99．99998 HFC-134 ( ％ ) 99．99999 99．99999 99．99999 99．99999 HFC-134 RECOV．EFF． ( ％ ) 64．3 83．5 91．9 91．9
In these embodiments, operate distillation tower under certain distillation temperature condition, thereby form the PFC-C318/HFC-134 Azeotrope compositions, wherein the concentration of HFC-134 is less than the concentration in adding material mixture.Lower boiling HFC-134/PFC-C318 azeotrope becomes the cat head effluent and the HFC-134 that surpasses described Azeotrope compositions amount that adds obtains reclaiming in bottom stream.
Along with the reduction of the increase distillation rate of reflux rate, the efficient of excessive separation HFC-134 increases in distillation tower, can reclaim this excessive HFC-134 that does not have PFC-C318 substantially like this in comparative example 14,15,16 and 17.Yet the increase of this efficient requires to enlarge markedly reflux rate, and significantly reduces the distillate generating rate.In addition, the HFC-134 of some addings must be retained in a part that becomes the PC-C318/HFC-134 Azeotrope compositions in the distillate, has limited the possible rate of recovery (by this component distillation) of HFC-134.
Yet, these comparative examples show that the lower boiling Azeotrope compositions that how will contain PFC-C318 and HFC-134 is used to shift out PFC-C318 from the original mixture that contains PFC-C318 and HFC-134, thereby can not had the HFC-134 product stream of PFC-C318 substantially.
Comparative example 18 and 19
In comparative example 18 and 19, will contain PFC-C318 and C under certain condition 4F 10Feed stream add distillation tower, as shown in table 6.To contain perfluor hexane (C 6F 14) extraction agent stream be higher than PFC-C318/C 4F 10The feed point of feed point add in the described tower with extraction fluidic form.These distillatory the results are shown in table 6.
6 18 19 C6F14 C6F14 92 92 10 10 40 40TOP TEMP ( ℃ ) 7．3 7．3REFLUX TEMP ( ℃ ) 7．3 7．3DIST TEMP ( ℃ ) 7．3 7．3BTMS TEMP ( ℃ ) 74．8 75．4EXTR FEED TEMP ( ℃ ) 10．0 10．0FEED TEMP ( ℃ ) 10．5 10．5TOP PRES ( PSIA ) 24．7 24．7CONDSR PRES ( PSIA ) 24．7 24．7BTMS PRES ( PSIA ) 27．7 27．7 ( PPH ) 25．0 250．0 ( PPH ) 3000． 3000． ( PPH ) 100975． 100750． ( PPH ) 100000． 100000． ( LB-MOLES／HR ) 295．8 295．8 ( PCU／HR ) -79435．-85343． ( PCU／HR ) +1730243． +1746685． PFC-C318 ( PPH ) 980． 980． C4F 10(PPH) 20. 20. EXTR. (PPH) 0. 0. form C 4F 10(PPM-weight) 20000. 20000. C 4F 10(PPM-mole) 16861. 16861. extraction tower distillate flow PFC-C318 (PPH) 25.00 249.97 C 4F 10(PPH) 0.00 0.03 EXTR. (PPH) 0.00 0.00 forms C 4F 10(PPM-mole) 64. 104. PFC-C318 (weight %) 99.99235 99.98764 PFC-C318 (mole %) 99.99357 99.98961 extraction tower underflows go out logistics capacity PFC-C318 (PPH) 955. 730. C 4F 10(PPH) 20.00 19.97 EXTR. (PPH) 100000. 100000. form C 4F 10(PPM-mole) 17293. 22471. PFC-C318 (weight %) 97.94891 97.33745 PFC-C318 (mole %) 98.27068 97.75294 PFC-C318 RECOV.EFF. (%) 97.45 74.49
In comparative example 18 and 19, the composition of feed streams is identical with comparative example 1,2 and 3.Although adopt high extraction agent to add speed, very high tower and high reflux rate, C among the product P FC-C318 4F 10Concentration only reduce to and be slightly less than 100ppmm.Comparative example 18 and 19 shows, and is used for isolating conventional distillation in the comparative example 1,2 and 3 and compares, and uses extraction agent C 6F 14There is not advantage.C 6F 14Be that many helping by extractive distillation makes separation PFC-C318 and C 4F 10An example of invalid extraction agent.
Embodiment 20 to embodiment 31
In embodiment 20 to embodiment 31, will contain HFC-C318 and C 4F 10Raw materials stream add distillation tower and operate under certain condition, as shown in table 7.The HFC-C318 and the C of feed streams in each example of embodiment 20 to embodiment 31 4F 10Concentration and comparative example 1,2,3,18 and 19 identical.
In each example of embodiment 20 to embodiment 31, different compounds is added described tower with the form of extraction agent.Operate described distillation tower in these embodiments and from tower, remove C with the form of overhead distillate 4F 10, and reclaim product HFC-C318 with the form of bottom stream.The extraction agent of each embodiment and described distillatory the results are shown in table 7.
7 20 21 22 23 24 25 26 MEK THF 1,4- 72 72 72 72 72 72 72 15 15 15 5 10 10 10 30 30 35 20 20 20 20TOP TEMP ( ℃ ) 37．7 40．5 40．5 40．6 40．3 40．5 37．7REFLUX TEMP ( ℃ ) 37．6 40．3 40．3 40．3 40．1 40．3 37．5DIST TEMP ( ℃ ) 37．6 40．3 40．3 40．3 40．1 40．3 37．5BTMS TEMP ( ℃ ) 53．2 88．9 74．3 70．2 76．0 99．1 65．2EXTR FEED TEMP ( ℃ ) 40．0 40．0 40．0 40．0 40．0 40．0 40．0FEED TEMP ( ℃ ) 38．1 38．1 38．1 38．1 38．1 38．1 38．1TOP PRES ( PSIA ) 64．7 64．7 64．7 64．7 64．7 64．7 64．7CONDSR PRES ( PSIA ) 64．7 64．7 64．7 64．7 64．7 64．7 64．7BTMS PRES ( PSIA ) 67．7 67．7 67．7 67．7 67．7 67．7 67．7 ( PPH ) 25．9 25．1 25．2 25．0 25．7 25．0 25．3 ( PPH ) 3000． 3000． 3000． 3000． 3000． 3000． 3000． ( PPH ) 5034． 9761． 10344． 13361． 19118． 22239． 15679． ( PPH ) 4060． 8786． 9369． 12386． 18144． 21264． 14704． ( LB-MOLES／HR ) 69．9 121．9 129．9 140 6 152．0 353．8 458．9 ( PCU／HR )-72400．-61347．-62079．-61072．-63803．-61537．-70007． ( PCU／HR ) +105352． +312053． +213459． +245962． +227529． +1004089． +316004． PFC-C318 ( PPH ) 980． 980． 980． 980． 980． 980． 980． C4F 10(PPH) 20. 20. 20. 20. 20. 20. 20. EXTR. (PPH) 0. 0. 0. 0. 0. 0. 0. form C 4F 10(PPM-weight) 20000. 20000. 20000. 20000. 20000. 20000. 20000. C 4F 10(PPM-mole) 16861. 16861. 16861. 16861. 16861. 16861. 16861. extraction tower distillate PFC-C318 (PPH) 5.00 5.00 5.00 5.00 5.00 5.00 5.00 C 4F 10(PPH) 20.0 20.0 20.0 20.0 20.0 20.0 20.0 EXTR., (PPH) 0.95 0.07 0.16 0.05 0.71 0.05 0.30 extraction bottom stream PFC-C318, (PPH) 975. 975. 975. 975. 975. 975. 975. C 4F 10(PPH) 0.00116 0.00116 0.00116 0.00116 0.00116 0.00116 0.00116 EXTR. (PPH), 4059. 8786. 9369. 12386. 18143. 21264. 14704. composition-(value that does not comprise extraction agent) C 4F 10(PPM-mole) 1.0 1.0 1.0 1.0 1.0 1.0 1.0 PFC-C318, (% by weight) 99.99988 99.99988 99.99988 99.99988 99.99988 99.99988 99.99988 PFC-C318, (% by mole) 99.99990 99.99990 99.99990 99.99990 99.99990 99.99990 99.99990PFC-C318RECOV.EFF., (%) 99.49 99.49 99.49 99.49 99.49 99.49 99.49
7 ( ) 27 28 29 30 31 MTBE CYANE DEE 92 92 92 92 92 15 5 5 5 5 35 25 25 35 35 ( ℃ ) 10．5 10．6 10．5 8．9 10．7 ( ℃ ) 10．3 10．3 10．3 8．8 10．4 ( ℃ ) 10．3 10．3 10．3 8．8 10．4 ( ℃ ) 63．2 52．1 51．4 47．5 85．1EXTR FEED TEMP ( ℃ ) 10．0 10．0 10．0 10．0 10．0FEED ( ℃ ) 10．5 10．5 10．5 10．5 10．5 ( PSIA ) 24．7 24．7 24．7 24．7 24．7 ( PSIA ) 24．7 24．7 24．7 24．7 24．7 ( PSIA ) 27．7 27．7 27．7 27．7 27．7 ( PPH ) 25．1 25．0 25．0 26．5 25．2 ( PPH ) 3000． 3000． 3000． 3000． 3000． ( PPH ) 20359． 19668． 24543． 29256． 60205． ( PPH ) 19385． 18694． 23568． 28283． 59231． ( LB-MOLES／HR ) 219．9 222．1 255．8 381．6 687．4 ( PCU／HR ) -69856．-69242．-68832．-81060．-70072． ( PCU／HR ) +619018． +430629． +479421． +696617． +2617593PFC-C318／C4F10 PFC-C318 ( PPH ) 980． 980． 980． 980． 980． C4F 10(PPH) 20. 20. 20. 20. 20. EXTR. (PPH) 0. 0. 0. 0. 0. form C 4F 10(PPM-weight) 20000. 20000. 20000. 20000. 20000. C 4F 10(PPM-mole) 16861. 16861. 16861. 16861. 16861. extraction tower distillate flow PFC-C318 (PPH) 5.00 5.00 5.00 5.00 5.00 C 4F 10(PPH) 20.0 20.0 20.0 20.0 20.0 EXTR. (PPH), 0.15 0.05 0.00 1.48 0.16 extraction tower underflow goes out logistics capacity PFC-C318 (PPH) 975. 975. 975. 975. 975. C 4F 10(PPH) 0.00116 0.00116 0.00116 0.00116 0.00116 extraction agents (PPH), 19384. 18693. 23568. 28281. 59230. composition-(value that does not comprise extraction agent) C 4F 10(PPM-mole) 1.0 1.0 1.0 1.0 1.0 PFC-C318, (weight %) 99.99988 99.99988 99.99988 99.99988 99.99988 PFC-C318, (mole %) 99.99990 99.99990 99.99990 99.99990 99.99990 PFC-C318 RECOV.EFF., (%) 99.49 99.49 99.49 99.49 99.49
By these embodiment and comparative example 1,2,3 and comparative example 18 and 19 are compared, can find that the extraction agent in the comparative example 20 to 33 has obviously increased the separation distillation efficiency, therefore for being used for separation of C from PFC-C318 4F 10Effective extracting.Among the embodiment 20 to 31, add to become a mandarin with raw material and compare C 4F 10The PFC-C318 that concentration obviously reduces obtains reclaiming from the form of base product with the PFC-C318 product.Since extremely difficulty maybe can not obtain C in comparative example 4F 10Concentration is lower than the PFC-C318 product of 10ppmm, and the PFC-C318 product rate of recovery that so can be high in each embodiment of table 7 obtains C 4F 10Concentration is lower than the PFC-C318 product of 1ppmm.
Press from separating PFC-C318/C 4F 10Most effectively list 11 kinds of extraction agents to the minimum order of efficient, most effective be defined as to be used for producing contain 1ppmm C 4F 10The required molar flow of the extraction agent of product P FC-C318 less.Based on this, the order from efficient " the highest " to the extraction agent of " minimum " is: acetone, methylethylketone (MEK), tetrahydrofuran (THF) (THF), 1,4-diox, chloroform (CHCl 3), methyl alcohol, methyl tertiary butyl ether (MTBE), hexanaphthene (CYANE), toluene, ether (DEE) and normal hexane.Compare with the routine distillation in the comparative example 1,2 and 3, all these extraction agents have been put upside down PFC-C318 and C 4F 10Normal relative volatility, thereby in the presence of extraction solvent C 4F 10Form with distillate stream obtains reclaiming, and PFC-C318 obtains reclaiming with the form of extractive distillation tower bottom effluent.Among the embodiment 20 to 33 each example show can choose wantonly by the distillation or other method from bottom stream, described extraction agent is separated with PFC-C318.
Though belonging to, acetone is used for separating PFC-C318/C 4F 10Effective extracting, but acetone and PFC-C318 form lower boiling azeotrope.Though MEK, THF and 1, the 4-diox separates PFC-C318 and C 4F 10Efficient basic identical, but in extraction tower, MEK and 1,4-diox and PFC-C318 two kinds of liquid phases of formation and require bigger extraction agent flow have increased the difficulty of operating described tower.Being used for this isolating extraction agent and most preferably being followed successively by THF, is MEK and 1 subsequently, the 4-diox.
Embodiment 32
In this embodiment, will contain PFC-C318 and C 4F 10Stream add extraction distillation column, wherein with THF with the form of extraction agent from being higher than PFC-C318/C 4F 10The feed point of feed point add described tower.To add stripping tower from the bottom stream that contains PFC-C318 and THF of extraction tower subsequently.In described stripping tower, form that can product of distillation is not had C substantially 4F 10With the PFC-C318 of extraction agent THF, and extraction agent THF returns it to extraction tower with the reinforced form circulation of extraction agent subsequently with the form recovery of bottom stream.These distillatory operational conditions and the results are shown in table 8.
8 72 42 15 35 35TOP TEMP ( ℃ ) 40．5 TOP TEMP ( ℃ ) 7．4REFLUX TEMP ( ℃ ) 40．3 REFLUX TEMP ( ℃ ) 7．3DIST TEMP ( ℃ ) 40．3 DIST TEMP ( ℃ ) 7．3BTMS TEMP ( ℃ ) 74．3 BTMS TEMP ( ℃ ) 85．6EXTR FEED TEMP ( ℃ ) 40．0 FEED TEMP ( ℃ ) 74．3FEED TEMP ( ℃ ) 38．1 FEED TEMPTOP PRES ( PSIA ) 64．7 TOP PRES ( PSIA ) 24．7CONDSR PRES ( PSIA ) 64．7 CONDSR PRES ( PSIA ) 24．7BTMS PRES ( PSIA ) 67．7 BTMS PRES ( PSIA ) 26．7 ( PPH ) 25．2 ( PPH ) 975．0 ( PPH ) 3000． ( PPH ) 4282． ( PPH ) 10344． ( PPH ) 9369． ( PPH ) 9369． ( LB-／ ) 129．9 PFC-C318 ( PPH ) 980． PFC-C318 ( PPH ) 975． C4F 10(PPH) 20. C4F10 (PPH), 0.0117 EXTR. (PPH), 0. EXTR. (PPH) 9368. form C 4F 10(PPM-weight) 20000. C 4F 10Distillate flow flow PFC-C318 (PPH) 5.00 PFC-C318 (PPH) 975. C of the distillate stripping tower of (PPM-mole) 16861. extraction towers 4F 10(PPH) 20.0 C4F10, (PPH) 0.117E-02 EXTR., (PPH) 0.16 EXTR., (PPH) 0.176E-04 forms PFC-C318, (mole %) 99.99989 C 4F 10Effluent stripper bottom, (PPM-mole) 1.0 EXTR. (PPM-mole) 0.05 PFC-C318 RECOV.EFF (%) 99.49 extraction towers bottom effluent stream amount flow PFC-C318 (PPH) 975. PFC-C318 (PPH) 0.5 C4F 10(PPH) 0.00117 C4F10 (PPH) 0.676E-08 EXTR. (PPH), 9368. EXTR. (PPH) 9368.
This embodiment shows that how using extractive distillation of the present invention to produce with the high PFC-C318 rate of recovery does not have C substantially 4F 10The product P FC-C318 of agent is got in steaming with THF.C by PFC-C318 that contains 980pph and 20pph 4F 10Feed streams be starting point, obtain containing the C of 1.0ppmm 4F 10With the product P FC-C318 of the THF of 0.05ppmm, the rate of recovery of PFC-C318 is 99.5%.
Embodiment 33
Table 9 shows extractive distillation and the stripping step of the raw material PFC-C318 that contains CFC-114, HCFC-124a, CFC-217ba and PFC-1318my halo impurity of being used for purifying.Used extraction agent is THF.Described product P FC-C318 reclaims with the form of basic Halogen for the extraction tower distillate of impurity and THF.Halo impurity reclaims with the form of extraction bottom stream with THF, and this bottom stream adds in the stripping tower with reinforced form subsequently.Described stripping tower is removed organic impurity from THF, described organic impurity reclaims with the form of stripping tower distillate, and THF then reclaims with the form of stripping bottom stream, returns described extraction tower with the reinforced form circulation of extraction agent subsequently.
9 72 42 40 25 55TOP TEMP ( ℃ ) 7．4 ( ℃ ) 11．3REFLUX TEMP ( ℃ ) 7．3 ( ℃ ) 8．6DIST TEMP ( ℃ ) 7．3 ( ℃ ) 8．6BTMS TEMP ( ℃ ) 86．3 BTMS TEMP ( ℃ ) 85．6EXTR FEED TEMP ( ℃ ) 5．0 ( ℃ ) 87．2FEED TEMP ( ℃ ) 10．5TOP PRES ( PSIA ) 24．7 ( PSIA ) 24．7CONDSR PRES ( PSIA ) 24．7 ( PSIA ) 24．7BTMS PRES ( PSIA ) 27．7 ( PSIA ) 26．7 ( PPH ) 993．9 ( PPH ) 6．2 ( PPH ) 5000． ( PPH ) 4274． ( PPH ) 7995． ( PPH ) 7989． ( PPH ) 7989． ( LB-／ ) 110．8 PFC-C318 ( PPH ) 998．9 PFC-C318 ( PPH ) 5．0 CFC-114 ( PPH ) 1．0 CFC-114 ( PPH ) 1．0 HCFC-124a ( PPH ) 0．200E-01 HCFC-124a ( PPH ) 0．220E-01 CFC-217ba ( PPH ) 0．10 CFC-217ba ( PPH ) 0．10 PFC-1318my ( PPH ) 0．200E-01 PFC-1318my ( PPH ) 0．200E-01 EXTR． ( PPH ) 0．0 EXTR． ( PPH ) 7989．0 ( PPM- ) 1140．0 ( PPM- ) 1317．2 PFC-C318 ( PPH ) 993．9 PFC-C318 ( PPH ) 5．0 EXTR． ( PPH ) 0．678E-06 EXTR． ( PPH ) 0．10 CFC-114 ( PPH ) 1．0 CFC-114 ( PPM- ) 0．694E-02 HCFC-124a ( PPH ) 0．200E-01 HCFC-124a ( PPM- ) 0．202E-01 CFC-217ba ( PPH ) 0．990E-01 CFC-217ba ( PPM- ) 0．966E+00 PFC-1318my ( PPH ) 0．200E-01 PFC-1318my ( PPM- ) 0．496E-02 EXTR． ( PPM- ) 0．189E-02 ( PPM- ) 0．100E+01 PFC-C318 ( ％ ) 99．999899 PFC-C318 ( ％ ) 99．999900 PFC-C318 RECOV EFF． ( ％ ) 99．50 PFC-C318 ( PPH ) 5．0 PFC-C318 ( PPH ) 0．385E-17 CFC-114 ( PPH ) 1．0 CFC-114 ( PPH ) 0．185E-03 HCFC-124a ( PPH ) 0．220E-01 HCFC-124a ( PPH ) 0．200E-02 CFC-217ba ( PPH ) 0．10 CFC-217ba ( PPH ) 0．190E-14 PFC-1318my ( PPH ) 0．200E-01 PFC-1318my ( PPH ) 0．924E-15 EXTR． ( PPH ) 7989． EXTR． ( PPH ) 7989．
Embodiment 34-40
Table 10 shows 7 kinds of different extraction solvents is used for removing the step that PFC-C318 obtains pure substantially HFC-134 from HFC-134.By PFC-C318/HFC-134 is most effective to sort to these 7 kinds of extraction agents to the minimum order of efficient from separating, most effectively be defined as the tower bottom flow of producing the PFC-C318 that contains 0.1ppm to go out the molar flow of the required extraction agent of product HFC-134 less.Based on this, be from the order of efficient " the highest " to " minimum ": 1,4-diox, tetrahydrofuran (THF) (THF), methylethylketone (MEK), methyl tertiary butyl ether (MTBE), methyl alcohol, toluene and propyl alcohol.PFC-C318 reclaims with the form of not having HFC-134 and extraction agent substantially in distillate stream in the presence of extraction solvent, and HFC-134 reclaims with the form that the extractive distillation tower bottom flow goes out thing with extraction agent.The extraction agent of pointing out can be chosen wantonly subsequently by distillation or other method and separate from HFC-134.
10 34 35 36 37 38 39 40 1,4- THF MEK MTBE 62 62 62 62 62 62 62 8 8 8 8 8 8 8 20 20 25 20 20 20 20TOP TEMP ( ℃ ) 7．4 7．4 7．4 7．5 6．5 7．4 7．4REFLUX TEMP ( ℃ ) 7．3 7．3 7．3 7．3 6．5 7．3 7．3DIST TEMP ( ℃ ) 7．3 7．3 7．3 7．3 6．5 7．3 7．3BTMS TEMP ( ℃ ) 30．3 31．1 43．1 29．0 10．0 17．7 21．8EXTR FEED TEMP ( ℃ ) 5．0 5．0 5．0 5．0 5．0 5．0 5．0FEED TEMP ( ℃ ) -5．2-5．2-5．2-5．2-5．2-5．2-5．2TOP PRES ( PSIA ) 24．7 24．7 24．7 24．7 24．7 24．7 24．7CONDSR PRES ( PSIA ) 24．7 24．7 24．7 24．7 24．7 24．7 24．7BTMS PRES ( PSIA ) 27．7 27．7 27．7 27．7 27．7 27．7 27．7 ( PPH ) 50．0 50．0 50．0 50．2 50．3 50．0 50．0 ( PPH ) 300． 300． 300． 300． 300． 300． 300． ( PPH ) 2245． 2156． 2382． 2780． 1748． 3540． 4776． ( PPH ) 1295． 1206． 1432． 1830． 798． 2590． 3826． ( LB-MOLES／HR ) 14．7 16．7 19．9 20．8 24．9 28．1 63．7 PFC-C318 ( PPH ) 50． 50． 50． 50． 50． 50． 50． HFC-134 ( PPH ) 950． 950． 950． 950． 950． 950． 950． EXTR． ( PPH ) 0． 0． 0． 0． 0． 0． 0． PFC-C318 ( PPM- ) 50000． 50000． 50000． 50000． 50000． 50000． 50000． PFC-C318 ( PPM- ) 26144． 26144． 26144． 26144． 26144． 26144． 26144． PFC-C318 ( PPH ) 50．00 50．00 50．00 50．00 50．00 50．00 50．00 HFC-134 ( PPH ) 0．01 0．01 0．01 0．01 0．01 0．01 0．01 EXTR． ( PPH ) 0．124E-4 0．346E-1 0．293E-1 0．143 0．307 0．159E-3 0．544E-8 PFC-C318 ( PPH ) 0．00019 0．00019 0．00019 0．00019 0．00019 0．00019 0．00019 HFC-134 ( PPH ) 950． 950． 950． 950． 950． 950． 950． EXTR． ( PPH ) 1295． 1206． 1432． 1830． 798． 2590． 3826． - ( ) PFC-C318 ( PPM- ) 0．1 0．1 0．1 0．1 0．1 0．1 0．1 HFC-134 ( ％ ) 99．99998 99．99998 99．99998 99．99998 99．99998 99．99998 99．99998 HFC-134 ( ％ ) 99．99999 99．99999 99．99999 99．99999 99．99999 99．99999 99．99999 HFC-134 RECOV．EFF． ( ％ ) 100．00 100．00 100．00 100．00 100．00 100．00 100．00
Embodiment 41,42
Table 11 is listed the operational condition and the result of embodiment 41 and 42.These embodiment describe and carry out extractive distillation with THF as extraction agent, and wherein PFC-C318 and HFC-134 obtain recovery respectively from the mixture of the PFC-C318 (24.9% (mole)) of the HFC-134 (75.1% (mole)) that contains 60.6% (weight) and 39.4% (weight).This feed composition contains the Azeotrope compositions that is formed by HFC-134 and PFC-C318 under these distillation temperatures.Shown in comparative example 6,7,8 and 9, in fact can not separate described HFC-134 and PFC-C318 Azeotrope compositions by the routine distillation.
Yet embodiment 41 and 42 shows that use THF makes extractive distillation can be used for separating as extraction agent.In embodiment 41, product P FC-C318 reclaims with the form of the distillation tower distillate that contains 0.1ppmm total impurities (HFC-134 and THF), and the product P FC-C318 of recovery is greater than 99% of the PFC-C318 that adds described tower.In embodiment 42, product HFC-134 contains the PFC-C318 of 0.1ppmm, and the product HFC-134 that reclaims be substantially the described tower of adding HFC-134 100%.
11 41 42 THF THF 62 62 40 15 50 30TOP TEMP ( ℃ ) 7．4 7．4REFLUX TEMP ( ℃ ) 7．3 7．3DIST TEMP ( ℃ ) 7．3 7．3BTMS TEMP ( ℃ ) 49．4 31．4EXTR FEED TEMP ( ℃ ) 5．0 5．0PFC-C318 FEED TEMP ( ℃ ) -7．3-7．3TOP PRES ( PSIA ) 24．7 24．7CONDSR PRES ( PSIA ) 24．7 24．7BTMS PRES ( PSIA ) 27．7 27．7 ( PPH ) 392．0 394．2 ( PPH ) 1231． 600． ( PPH ) 2191． 1385． ( PPH ) 1583． 779． ( LB-MOLES／HR ) 22．0 10．8 ( PCU／HR ) -42621．-26149． ( PCU／HR ) 83981． 43128． PFC-C318 ( PPH ) 394．0 394．0 HFC-134 ( PPH ) 606．0 606．0 HFC-134 ( PPM- ) 606000．0 606000．0 HFC-134 ( PPM- ) 750956．6 750956．6 PFC-C318 ( PPH ) 392．0 394．0 HFC-134 ( PPH ) 0．999E-05 0．01 EXTR． ( PPH ) 0．706E-05 0．177 HFC-134 ( PPM- ) 0．05 49．7 EXTR． ( PPM- ) 0．05 1250 ( PPM- ) 0．10 1300 PFC-C318 ( ％ ) 99．999996 99．95 PFC-C318 ( ％ ) 99．999990 99．87 PFC-C318 RECOV．EFF ( ％ ) 99．49 100．00 PFC-C318 ( PPH ) 2．0 0．0 HFC-134 ( PPH ) 606．0 606．0 EXTR． ( PPH ) 1583． 779． - ( ) PFC-C318 ( PPM- ) 1680 0．10 HFC-134 ( ％ ) 99．67 99．99998 HFC-134 ( ％ ) 99．83 99．99999 HFC-134 RECOV．EFF． ( ％ ) 100．00 100．00
Embodiment 43,44
In embodiment 43 and 44, the stream that will contain PFC-C318 and C4F10 adds extraction distillation column, wherein with THF as extraction agent to be higher than PFC-C318/C 4F 10The feed point of feed point add described tower.These distillatory operational conditions and the results are shown in table 12.
12 43 44 THF THF 72 72 15 15PFC-C318 35 35TOP TEMP ( ℃ ) 40．5 40．5REFLUX TEMP ( ℃ ) 40．3 40．3DIST TEMP ( ℃ ) 40．3 40．3BTMS TEMP ( ℃ ) 74．3 82．7EXTR FEED TEMP ( ℃ ) 40．0 40．0FEED TEMP ( ℃ ) 38．1 38．1TOP PRES ( PSIA ) 64．7 64．7CONDSR PRES ( PSIA ) 64．7 64．7BTMS PRES ( PSIA ) 67．7 67．7 ( PPH ) 25．2 25．2 ( PPH ) 3000． 3000． ( PPH ) 10344． 13742． ( PPH ) 9369． 12767． ( LB-MOLES／HR ) 129．9 177．1 ( PCU／HR ) -62079．-62089． ( PCU／HR ) +213459． +316903． PFC-C318 ( PPH ) 980． 980． C4F 10(PPH) 20. 20. EXTR. (PPH) 0. 0. form C 4F 10(PPM-weight) 20000. 20000. C 4F 10(PPM-mole) 16861. 16861. extraction tower distillate flow PFC-C318 (PPH) 5.00 5.00 C 4F 10(PPH) 20.0 20.0 EXTR. (PPH), 0.16 0.16 extraction tower underflow goes out logistics capacity PFC-C318 (PPH) 975. 975. C 4F 10(PPH) 0.00116 0.00116 EXTR. (PPH), 9369. 12767. composition-(value that does not comprise extraction agent) C 4F 10(PPM-mole) 1.0 0.1 PFC-C318 (weight %) 99.99988 99.99999 PFC-C318 (mole %) 99.99990 99.99999 PFC-C318 RECOV.EFF. (%) 99.49 99.49
Embodiment 43 is identical with the embodiment 22 of front, and to contain 1.0ppmm C 4F 10The form of extraction tower underflow of PFC-C318 produce the PFC-C318 product, the rate of recovery of PFC-C318 is 99.5%.Compare with embodiment 43, the extraction agent flow that flows to described tower among the embodiment 44 increases, and to contain 0.1ppmm C 4F 10The form of extraction tower underflow of PFC-C318 to produce the rate of recovery be 99.5% product P FC-C318.
Embodiment 45
This embodiment illustrates mainly in the paired mixture of being made up of following material of binary and has azeotropic or Azeotrope-like compositions that they are PFC-C318 and HCFC-124; PFC-C318 and HCFC-124a; PFC-C318 and HFC-134; PFC-C318 and HFC-134a and PFC-C318 and HFC-152a.Adopt the PTx method to calculate the relative volatility of every pair of material.In this method, the various binary compositions that oneself knows are measured the total absolute pressure in the sample pool of known volume under constant temp.Use the NRTL equation to derive the equilibrium composition of steam and liquid by these observed values subsequently.
The vapor pressure observed value of the composition of these binary systems is shown in Fig. 3 respectively to Fig. 7 in the corresponding PTx pond.Experimental data point is represented with the solid dot among each figure, and the data of using the NRTL equation to calculate are made solid wire.
Referring now to Fig. 2, Fig. 2 is shown in forming of the 20 ℃ of azeotropic is made up of PFC-C318 and HCFC-124 down mainly and Azeotrope-like compositions, points out the mixture pressure maximum of the HCFC-124 of the PFC-C318 and 73.1% (mole) that consists of 26.9% (mole) in the scope at this composition under this temperature.Based on these discoveries, can calculate azeotropic or the Azeotrope-like compositions of the HCFC-124 of the PFC-C318 and 73.1% (mole) that under 0 ℃ and 24psia, forms 26.9% (mole), and 80 ℃ with 234psia under form azeotropic or the Azeotrope-like compositions of HCFC-124 of the PFC-C318 and 72.5% (mole) of 27.5% (mole).Correspondingly, the invention provides mainly azeotropic or Azeotrope-like compositions that the HCFC-124 by the PFC-C318 of 26.9-27.5% (mole) and 73.1-72.5% (mole) forms, the boiling point of described composition is under the 24psia 0 ℃ under the 234psia 80 ℃.
Referring now to Fig. 3, Fig. 3 is shown in 20 ℃ of azeotropic and Azeotrope-like compositions of mainly being made up of PFC-C318 and HCFC-124a down, points out the mixture pressure maximum of the HCFC-124a of the PFC-C318 and 67.6% (mole) that consists of 22.4% (mole) in the scope at this composition under this temperature.Based on these discoveries, can calculate azeotropic or the Azeotrope-like compositions of the HCFC-124a of the PFC-C318 and 66.9% (mole) that under 0 ℃ and 24psia, forms 33.1% (mole), and 80 ℃ with 229psia under form azeotropic or the Azeotrope-like compositions of HCFC-124a of the PFC-C318 and 66.1% (mole) of 33.9% (mole).Correspondingly, the invention provides mainly azeotropic or Azeotrope-like compositions that the HCFC-124a by the PFC-C318 of 33.1-33.9% (mole) and 66.9-66.1% (mole) forms, the boiling point of described composition is under the 24psia 0 ℃ under the 229psia 80 ℃.
Referring now to Fig. 4, Fig. 4 is shown in 0 ℃ of azeotropic and Azeotrope-like compositions of mainly being made up of PFC-C318 and HFC-134 down, points out the mixture pressure maximum of the HFC-134 of the PFC-C318 and 75.0% (mole) that consists of 25.0% (mole) in the scope at this composition under this temperature.Based on these discoveries, can calculate azeotropic or the Azeotrope-like compositions of the HFC-134 of the PFC-C318 and 75.4% (mole) that under-30 ℃ and 10psia, forms 24.6% (mole), and 80 ℃ with 326psia under form azeotropic or the Azeotrope-like compositions of HFC-134 of the PFC-C318 and 76.8% (mole) of 23.2% (mole).Correspondingly, the invention provides mainly azeotropic or Azeotrope-like compositions that the HFC-134 by the PFC-C318 of 24.6-23.2% (mole) and 75.4-76.8% (mole) forms, the boiling point of described composition is-30 ℃ of under the 326psia 80 ℃ under the 10psia.
Referring now to Fig. 5, Fig. 5 is shown in 0 ℃ of azeotropic and Azeotrope-like compositions of mainly being made up of PFC-C318 and HFC-134a down, points out the mixture pressure maximum of the HFC-134a of the PFC-C318 and 92.6% (mole) that consists of 7.4% (mole) in the scope at this composition under this temperature.Based on these discoveries, can calculate azeotropic or the Azeotrope-like compositions of the HFC-134a of the PFC-C318 and 90.1% (mole) that under-30 ℃ and 12psia, forms 9.9% (mole), and 40 ℃ with 147psia under form azeotropic or the Azeotrope-like compositions of HFC-134a of the PFC-C318 and 99.4% (mole) of 0.6% (mole).Correspondingly, the invention provides mainly azeotropic or Azeotrope-like compositions that the HFC-134a by the PFC-C318 of 9.9-0.6% (mole) and 90.1-99.4% (mole) forms, the boiling point of described composition is-30 ℃ of under about 147psia 40 ℃ under the 12psia.
Referring now to Fig. 6, Fig. 6 is shown in 0 ℃ of azeotropic and Azeotrope-like compositions of mainly being made up of PFC-C318 and HFC-152a down, points out the mixture pressure maximum of the HFC-152a of the PFC-C318 and 76.9% (mole) that consists of 23.1% (mole) in the scope at this composition under this temperature.Based on these discoveries, can calculate azeotropic or the Azeotrope-like compositions of the HFC-152a of the PFC-C318 and 77.6% (mole) that under-20 ℃ and 19psia, forms 22.4% (mole), and 80 ℃ with 234psia under form azeotropic or the Azeotrope-like compositions of HFC-152a of the PFC-C318 and 78.7% (mole) of 21.3% (mole).Correspondingly, the present invention carries mainly azeotropic or the Azeotrope-like compositions that the HFC-152a by the PFC-C318 of 23.1-21.3% (mole) and 76.9-78.7% (mole) forms, and the boiling point of described composition is-20 ℃ of under the 349psia 80 ℃ under the 19psia.

Claims (19)

1. contain perfluorocyclobutane (PFC-C318) less than 10/1000000ths (mole) halo impurity.
2. contain perfluorocyclobutane (PFC-C318) less than 1,000,000/(mole) halo impurity.
3. contain perfluorocyclobutane (PFC-C318) less than 100/1000000000ths (mole) halo impurity.
4. azeotropic or Azeotrope-like compositions, mainly by the perfluorocyclobutane (PFC-C318) of 26.8-27.5% (mole) and the 2-chloro-1 of 73.1-72.5% (mole), 1,1,2-Tetrafluoroethane (HCFC-124) is formed, and the boiling point of described composition is 0 ℃ of 80 ℃ of arriving under the 234psia under the 24psia.
5. azeotropic or Azeotrope-like compositions, mainly by 1,1,2 of the perfluorocyclobutane (PFC-C318) of 24.6-23.2% (mole) and 75.4-76.8% (mole), 2-Tetrafluoroethane (HFC-134) is formed, and the boiling point of described composition is-30 ℃ of 80 ℃ of arriving under the 326psia under the 10psia.
6. azeotropic or Azeotrope-like compositions, mainly by 1,1,1 of the perfluorocyclobutane (PFC-C318) of 9.9-0.6% (mole) and 90.1-99.4% (mole), 2-Tetrafluoroethane (HFC-134a) is formed, and the boiling point of described composition is-30 ℃ of 40 ℃ of arriving under the 147psia under the 12psia.
7. azeotropic or Azeotrope-like compositions, mainly by 1 of the perfluorocyclobutane (PFC-C318) of 23.1-21.3% (mole) and 76.9-78.7% (mole), 1-C2H4F2 C2H4F2 (HFC-152a) is formed, and the boiling point of described composition is-20 ℃ of 80 ℃ of arriving under the 349psia under the 19psia.
8. the method for from the original mixture that contains perfluorocyclobutane (PFC-C318) and halo impurity, separating perfluorocyclobutane (PFC-C318), wherein the amount of perfluorocyclobutane (PFC-C318) is greater than the amount of perfluorocyclobutane (PFC-C318) in azeotropic that contains perfluorocyclobutane (PFC-C318) and impurity or Azeotrope-like compositions in the original mixture, and this method comprises:
The distillation original mixture forms second mixture, and it contains the azeotropic or the Azeotrope-like compositions of perfluorocyclobutane (PFC-C318) and impurity,
Form with the distillation overhead streams reclaims second mixture, and
Form with the base product effluent reclaims perfluorocyclobutane (PFC-C318).
9. the method for separating out at least one halo impurity from the original mixture that contains perfluorocyclobutane (PFC-C318) and halo impurity, wherein the amount of halo impurity is greater than the amount of halo impurity in azeotropic that contains perfluorocyclobutane (PFC-C318) and impurity or Azeotrope-like compositions in the original mixture, and this method comprises:
The distillation original mixture forms second mixture, and it contains the azeotropic or the Azeotrope-like compositions of perfluorocyclobutane (PFC-C318) and halo impurity,
Form with the distillation overhead streams reclaims second mixture, and
Form with the base product effluent reclaims halo impurity.
10. isolate the method for perfluorocyclobutane (PFC-C318) from halo impurity, be included under the existence of entrainment agent, distillation contains the mixture of perfluorocyclobutane (PFC-C318) and halo impurity.
11. the method for claim 10, wherein in the presence of entrainment agent, the relative volatility of perfluorocyclobutane (PFC-C318) or impurity increases.
12. separate the method for perfluorocyclobutane (PFC-C318) and halo impurity, comprising:
The original mixture that contains perfluorocyclobutane (PFC-C318) and halo impurity is contacted with entrainment agent form second mixture, and
Distill second mixture and reclaim and contain the distillation overhead streams of perfluorocyclobutane (PFC-C318) and contain entrainment agent and the base product effluent of impurity.
13. separate the method for perfluorocyclobutane (PFC-C318) and halo impurity, comprising:
The original mixture that contains perfluorocyclobutane (PFC-C318) and halo impurity is contacted with entrainment agent form second mixture, and
Distill second mixture and reclaim and contain the distillation overhead streams of halo impurity and contain entrainment agent and the base product effluent of perfluorocyclobutane (PFC-C318).
14. the method for claim 12 or 13, wherein original mixture comprises azeotropic or the Azeotrope-like compositions that contains perfluorocyclobutane (PFC-C318) and impurity.
15. claim 8,9,10,12 or 13 method, wherein halo impurity comprises a kind of of following material at least: PFC-31-10 (C 4F 10), PFC-41-12 (C 5F 12), PFC-1318my (cis or trans-CF 3CF=CFCF 3), PFC-1318c (CF 3CF 2CF=CF 2), PFC-1216 (CF 3CF=CF 2), PFC-1114 (CF 2=CF 2) perfluoroisobutylene (CF 2=C (CF 3) 2), CFC-114 (CF 2ClCF 2Cl), CFC-114a (CFCl 2CF 3), CFC-216ba (CF 3CFClCF 2Cl), CFC-217ba (CF 3CClFCF 3), CFC-1113 (CClF=CF 2), HCFC-124 (CHFClCF 3), HCFC-124a (CClF 2CHF 2), HFC-134 (CHF 2CHF 2), HFC-134a (CH 2FCF 3), HFC-152a (CH 3CF 2H), HFC-125 (CF 3CF 2H), HFC-227ca (CF 3CF 2CHF 2), HFC-227ea (CF 3CHFCF 3), HFC-1225zc (CF 3CH=CF 2), HFC-236ca (CHF 2CF 2CHF 2), HFC-236ea (CHF 2CHFCF 3), HFC-236fa (CF 3CH 2CF 3), HCC-30 (CH 2Cl 2), HCC-40 (CH 3Cl) and HCC-160 (CH 3CH 2Cl).
16. claim 10,12 or 13 method, wherein entrainment agent is selected from ethers, ketone, alcohols, hydro carbons and hydrochlorinate carbon.
17. the method for claim 16, wherein ethers is selected from methyl tertiary butyl ether, tetrahydrofuran (THF) and 1,4-diox; Ketone is selected from acetone and 2-butanone; Alcohols is selected from methyl alcohol and propyl alcohol; Hydrocarbon is selected from toluene and hexanaphthene; Hydrochlorinate carbon is selected from chloroform.
18. claim 8,10,12 or 13 method, the wherein perfluorocyclobutane of Hui Shouing (PFC-C318) substantially free of impurities.
19. claim 8,10,12 or 13 method, wherein the perfluorocyclobutane of Hui Shouing (PFC-C318) contains the impurity less than 10/1000000ths (moles).
CNB998036463A 1998-03-05 1999-03-05 Process for purifying perfluorocyclobutane Expired - Fee Related CN1183072C (en)

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US6333440B1 (en) 2000-04-07 2001-12-25 E. I. Du Pont De Nemours And Company Process for perfluorocyclobutane purification
TWI288025B (en) * 2000-09-14 2007-10-11 Showa Denko Kk Adsorbent for purifying perfluorocarbon, process for producing same, high purity octafluoropropane and octafluorocyclobutane, and use thereof
JP4767423B2 (en) * 2001-01-15 2011-09-07 昭和電工株式会社 Purification and production method of octafluorocyclobutane and use thereof
CN104529697B (en) * 2014-12-02 2016-05-25 山东东岳高分子材料有限公司 A kind of method that reclaims high-purity octafluorocyclobutane from monochlorodifluoromethane cracking raffinate
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