U.S. patent application number 13/403011 was filed with the patent office on 2013-08-29 for azeotropic compositions of 1,1,3,3-tetrachloro-1-fluoropropane and hydrogen fluoride.
The applicant listed for this patent is Ryan Hulse, Daniel C. Merkel, Hang T. Pham, Konstantin A. Pokrovski, Hsueh Sung Tung. Invention is credited to Ryan Hulse, Daniel C. Merkel, Hang T. Pham, Konstantin A. Pokrovski, Hsueh Sung Tung.
Application Number | 20130221273 13/403011 |
Document ID | / |
Family ID | 48999718 |
Filed Date | 2013-08-29 |
United States Patent
Application |
20130221273 |
Kind Code |
A1 |
Merkel; Daniel C. ; et
al. |
August 29, 2013 |
AZEOTROPIC COMPOSITIONS OF 1,1,3,3-TETRACHLORO-1-FLUOROPROPANE AND
HYDROGEN FLUORIDE
Abstract
Provided are azeotropic or azeotrope-like mixtures of
1,1,3,3-tetrachloro-1-fluoropropane (HCFC-241fa) and hydrogen
fluoride. Such compositions are useful as an intermediate in the
production of HFC-245fa and HCFO-1233zd.
Inventors: |
Merkel; Daniel C.; (West
Seneca, NY) ; Pokrovski; Konstantin A.; (Orchard
Park, NY) ; Pham; Hang T.; (Amherst, NY) ;
Tung; Hsueh Sung; (Getzville, NY) ; Hulse; Ryan;
(Getzville, NY) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Merkel; Daniel C.
Pokrovski; Konstantin A.
Pham; Hang T.
Tung; Hsueh Sung
Hulse; Ryan |
West Seneca
Orchard Park
Amherst
Getzville
Getzville |
NY
NY
NY
NY
NY |
US
US
US
US
US |
|
|
Family ID: |
48999718 |
Appl. No.: |
13/403011 |
Filed: |
February 23, 2012 |
Current U.S.
Class: |
252/183.11 ;
570/177; 62/617 |
Current CPC
Class: |
C11D 7/5045 20130101;
C09K 5/044 20130101; C07C 19/10 20130101; C09K 3/30 20130101 |
Class at
Publication: |
252/183.11 ;
570/177; 62/617 |
International
Class: |
C09K 3/00 20060101
C09K003/00; F25J 3/08 20060101 F25J003/08; C07C 17/38 20060101
C07C017/38 |
Claims
1. An azeotropic composition comprising effective amounts of
1,1,3,3-tetrachloro-1-fluoropropane (HCFC-241fa) and hydrogen
fluoride (HF).
2. The composition of claim 1, wherein the composition comprises
from about 99 to about 1 weight percent HF.
3. The composition of claim 1, wherein the composition comprises
from about 70 weight percent to about 99 weight percent HF.
4. The composition of claim 1, wherein the composition comprises
from about 70 weight percent to about 99 weight percent HF.
5. The composition of claim 1, wherein the composition comprises
from about 1 to about 99 weight percent HCFC-241fa.
6. The composition of claim 1, wherein the composition comprises
from about 70 weight percent to about 1 weight percent HCFC-241
fa.
7. The composition of claim 1, wherein the composition comprises
from about 30 weight percent to about 1 weight percent
HCFC-241fa.
8. The composition of claim 1, wherein the composition has a
boiling point of about from 21.degree. C. to about 60.degree. C. at
a pressure from about 16.5 psia to about 54.6 psia.
9. An azeotropic or azeotrope-like composition which includes about
98.+-.2 weight percent HF and about 2.+-.2 weight percent
HCFC-241fa and has a boiling point of about 21.degree. C. at 16.5
psia.
10. An azeotropic or azeotrope-like composition which consists
essentially of from about 90 to about 99 weight percent hydrogen
fluoride and from about 10 to about 1 weight percent
1,1,3,3-tetrachloro-1-fluoropropane (HCFC-241fa), which composition
has a boiling point of about 30.degree. C. to about 60.degree. C.
at pressure of about 21.4 psia to pressure of about 53.9 psia.
11. The composition of claim 10, which consists of hydrogen
fluoride and 1,1,3,3-tetrachloro-1-fluoropropane (HCFC-241fa).
12. A method of forming a heterogeneous azeotropic or
azeotrope-like composition comprising the step of blending
components which consist essentially of from about 1 to about 99
weight percent hydrogen fluoride and from about 99 to about 1
weight percent 1,1,3,3-tetrachloro-1-fluoropropane (HCFC-241fa),
which composition has a boiling point of about from 21.degree. C.
to about 60.degree. C. at pressure of about from 16.5 psia to about
54.6 psia.
13. The method of claim 12, wherein the composition consists of
hydrogen fluoride and 1,1,3,3-tetrachloro-1-fluoropropane
(HCFC-241fa).
14. The method of claim 12, wherein the composition comprises from
about 99 to about 1 weight percent HF.
15. The method of claim 12, wherein the composition comprises from
about 70 weight percent to about 99 weight percent HF.
16. The method of claim 12, wherein the composition comprises from
about 70 weight percent to about 99 weight percent HF.
17. The method of claim 12, wherein the composition comprises from
about 1 to about 99 weight percent HCFC-241fa.
18. The method of claim 12, wherein the composition comprises from
about 70 weight percent to about 1 weight percent HCFC-241fa.
19. The method of claim 12, wherein the composition comprises from
about 30 weight percent to about 1 weight percent HCFC-241fa.
20. The method of claim 12, wherein the composition has a boiling
point of about from 21.degree. C. to about 60.degree. C. at a
pressure from about 16.5 psia to about 54.6 psia.
21. The method of claim 12, wherein the composition consists of
about 98.+-.2 weight percent HF and about 2.+-.2 weight percent
HCFC-241fa, and has a boiling point of about 21.degree. C. at 16.5
psia.
22. A method of separating 241fa from the azeotropic like mixture
of 241 fa and HF comprising the step of extracting the HF from the
mixture.
23. The method of claim 22, wherein the extraction of HF is
accomplished using water or other aqueous solution.
24. The method of claim 22, wherein the extraction of HF is
accomplished using sulfuric acid.
25. The method of claim 22, wherein the extraction of HF is
accomplished by distillation.
26. The method of claim 25, wherein the distillation comprises
extractive distillation.
27. The method of claim 25, wherein the distillation comprises
pressure swing distillation.
Description
FIELD OF THE INVENTION
[0001] The present invention pertains to azeotropic or
azeotrope-like compositions of 1,1,3,3-tetrachloro-1-fluoropropane
(HCFC-241fa or 241fa) and hydrogen fluoride (HF).
BACKGROUND OF THE INVENTION
[0002] Chlorofluorocarbon (CFC) based chemicals have been widely
use in industry in a variety of different applications including as
refrigerants, aerosol propellants, blowing agents and solvents,
among others. However, certain CFCs are suspected of depleting the
Earth's ozone layer. Accordingly, more environmentally friendly
substitutes have been introduced as replacements for CFCs. For
example, 1,1,1,3,3-pentafluoropropane (HFC-245fa) is recognized as
having favorable physical properties for certain industrial
applications, such as foam blowing agents and solvents, and
therefore is consider to be a good substitute for the CFCs
previously used for these applications. Unfortunately, the use of
certain hydrofluorocarbons, including HFC-245fa, in industrial
applications is now believed to contribute to the global warming.
Accordingly, more environmentally friendly substitutes for
hydrofluorocarbons are now being sought.
[0003] The compound 1-chloro-3,3,3-trifluoropropene, also known as
HCFO-1233zd or simply 1233zd, is a candidate for replacing
HFC-245fa in some applications, including uses as blowing agents
and solvents. 1233zd has a Z-isomer and an E-isomer. Due to
differences in the physical properties between these two isomers,
pure 1233zd (E), pure 1233zd (Z), or certain mixtures of the two
isomers may be suitable for particular applications as
refrigerants, propellants, blowing agents, solvents, or for other
uses.
[0004] 1,1,3,3-Tetrachloro-1-fluoropropane (HCFC-241fa) is a
reactant used in the production of both 245fa and 1233zd. See for
example U.S. Pat. Nos. 5,763,706 and 6,844,475. See also, U.S.
Patent Publication No. 2011-0201853 which is directed to an
integrated process and methods of producing 1233zd (E).
[0005] It has now been found that an important intermediate in the
production of both 245fa and 1233zd, is an azeotrope or
azeotrope-like mixture of 1,1,3,3-tetrachloro-1-fluoropropane
(HCFC-241fa) and hydrogen fluoride (HF). This intermediate, once
formed, may thereafter be separated into its component parts, for
example by extraction or distillation techniques. HCFC-241fa has a
boiling point of about 140.2.degree. C. and HF has a boiling point
of about 20.degree. C. at standard atmospheric pressure. These
azeotropic or azeotrope-like compositions find use not only as
reactor feeds in the production of 245fa and 1233zd, but they are
additionally useful as solvent compositions for removing surface
oxidation from metals.
SUMMARY OF THE INVENTION
[0006] The present invention is directed to azeotropic or
azeotrope-like mixtures of 1,1,3,3-tetrachloro-1-fluoropropane
(HCFC-241fa) and hydrogen fluoride. Such compositions are useful as
an intermediate in the production of HFC-245fa and HCFO-1233zd.
[0007] In certain embodiments of this mixture, the composition
comprises effective amounts of 1,1,3,3-tetrachloro-1-fluoropropane
(HCFC-241fa) and hydrogen fluoride.
[0008] In certain embodiments of this mixture, the composition
comprises from about 99 to about 1 weight percent HF.
[0009] In certain embodiments of this mixture, the composition
comprises from about 70 weight percent to about 99 weight percent
HF.
[0010] In certain embodiments of this mixture, the composition
comprises from about 70 weight percent to about 99 weight percent
HF.
[0011] In certain embodiments of this mixture, the composition
comprises from about 1 to about 99 weight percent HCFC-241fa.
[0012] In certain embodiments of this mixture, the composition
comprises from about 70 weight percent to about 1 weight percent
HCFC-241 fa.
[0013] In certain embodiments of this mixture, the composition
comprises from about 30 weight percent to about 1 weight percent
HCFC-241 fa.
[0014] In certain embodiments of this mixture, the composition has
a boiling point of about from 21.degree. C. to about 60.degree. C.
at a pressure from about 16.5 psia to about 54.6 psia.
[0015] In another aspect of the invention there is provided a
heterogeneous azeotropic composition consisting essentially of
1,1,3,3-tetrachloro-1-fluoropropane (HCFC-241 fa) and hydrogen
fluoride (HF).
[0016] In certain embodiments of this mixture, the composition
consists essentially of from about 90 to about 99 weight percent
hydrogen fluoride and from about 10 to about 1 weight percent
1,1,3,3-tetrachloro-1-fluoropropane (HCFC-241fa), which composition
has a boiling point of about 30.degree. C. to about 60.degree. C.
at pressure of about 21.4 psia to pressure of about 53.9 psia.
[0017] Another aspect of the present invention is directed to a
method of forming a heterogeneous azeotropic or azeotrope-like
composition comprising the step of blending components which
consist essentially of from about 1 to about 99 weight percent
hydrogen fluoride and from about 99 to about 1 weight percent
1,1,3,3-tetrachloro-1-fluoropropane (HCFC-241fa), which composition
has a boiling point of about from 21.degree. C. to about 60.degree.
C. at pressure of about from 16.5 psia to about 54.6 psia.
[0018] In certain embodiments of this method, the composition
consists of hydrogen fluoride and
1,1,3,3-tetrachloro-1-fluoropropane (HCFC-241fa).
[0019] In certain embodiments of this method, the composition
comprises from about 99 to about 1 weight percent HF.
[0020] In certain embodiments of this method, the composition
comprises from about 70 weight percent to about 99 weight percent
HF.
[0021] In certain embodiments of this method, the composition
comprises from about 70 weight percent to about 99 weight percent
HF.
[0022] In certain embodiments of this method, the composition
comprises from about 1 to about 99 weight percent HCFC-241fa.
[0023] In certain embodiments of this method, the composition
comprises from about 70 weight percent to about 1 weight percent
HCFC-241 fa.
[0024] In certain embodiments of this method, the composition
comprises from about 30 weight percent to about 1 weight percent
HCFC-241 fa.
[0025] In certain embodiments of this method, the composition has a
boiling point of about from 21.degree. C. to about 60.degree. C. at
a pressure from about 16.5 psia to about 54.6 psia.
[0026] In certain embodiments of this method, the composition
consists of about 98.+-.2 weight percent HF and about 2.+-.2 weight
percent HCFC-241 fa, and has a boiling point of about 21.degree. C.
at 16.5 psia.
[0027] Another aspect of the present invention is directed to a
method of separating 241 fa from the azeotropic like mixture of 241
fa and HF comprising the step of extracting the HF from the
mixture.
[0028] In certain embodiments of this method, the extraction of HF
is accomplished using water or other aqueous solution.
[0029] In certain embodiments of this method, the extraction of HF
is accomplished using sulfuric acid.
[0030] In certain embodiments of this method, the extraction of HF
is accomplished by distillation.
[0031] In certain embodiments of this method, the distillation
comprises extractive distillation.
[0032] In certain embodiments of this method, the distillation
comprises pressure swing distillation.
BRIEF DESCRIPTION OF THE DRAWING
[0033] FIG. 1 shows a plot of the vapor pressures of the mixtures
formed in Example 1 as measured at 30.degree. C. and 60.degree.
C.
DETAILED DESCRIPTION OF THE INVENTION
[0034] When 1,1,3,3-tetrachloro-1-fluoropropane (HCFC-241fa) and HF
were fed to a reactor, it was found that the HCFC-241fa forms an
azeotropic or azeotrope-like mixture with HF. The unreacted
HCFC-241fa/HF intermediate was found in the product stream.
[0035] The thermodynamic state of a fluid is defined by its
pressure, temperature, liquid composition and vapor composition.
For a true azeotropic composition, the liquid composition and vapor
phase are essentially equal at a given temperature and pressure. In
practical terms this means that the components cannot be separated
during a phase change. For the purpose of this invention, an
azeotrope is a liquid mixture that exhibits a maximum or minimum
boiling point relative to the boiling points of surrounding mixture
compositions.
[0036] An azeotrope or an azeotrope-like composition is an
admixture of two or more different components which, when in liquid
form under given pressure, will boil at a substantially constant
temperature, which temperature may be higher or lower than the
boiling temperatures of the components and which will provide a
vapor composition essentially identical to the liquid composition
undergoing boiling.
[0037] For the purpose of this invention, azeotropic compositions
are defined to include azeotrope-like compositions, which means a
composition that behaves like an azeotrope, i.e., has
constant-boiling characteristics or a tendency not to fractionate
upon boiling or evaporation. Thus, the composition of the vapor
formed during boiling or evaporation is the same as or
substantially the same as the original liquid composition. Hence,
during boiling or evaporation, the liquid composition, if it
changes at all, changes only to a minimal or negligible extent.
This is in contrast with non-azeotrope-like compositions in which
during boiling or evaporation, the liquid composition changes to a
substantial degree.
[0038] Accordingly, the essential features of an azeotrope or an
azeotrope-like composition are that at a given pressure, the
boiling point of the liquid composition is fixed and that the
composition of the vapor above the boiling composition is
essentially that of the boiling liquid composition, i.e.,
essentially no fractionation of the components of the liquid
composition takes place. Both the boiling point and the weight
percentages of each component of the azeotropic composition may
change when the azeotrope or azeotrope-like liquid composition is
subjected to boiling at different pressures. Thus, an azeotrope or
an azeotrope-like composition may be defined in terms of the
relationship that exists between its components or in terms of the
compositional ranges of the components or in terms of exact weight
percentages of each component of the composition characterized by a
fixed boiling point at a specified pressure.
[0039] The present invention provides a composition which comprises
effective amounts of hydrogen fluoride and HCFC-241fa to form an
azeotropic or azeotrope-like composition. By effective amount is
meant an amount of each component which, when combined with the
other component, results in the formation of an azeotrope or
azeotrope-like mixture. The inventive compositions preferably are
binary azeotropes which consist essentially of combinations of only
hydrogen fluoride with HCFC-241fa.
[0040] In the preferred embodiment, the inventive composition
contains from about 99 to about 1 weight percent HF, preferably
from about 70 weight percent to about 99 weight percent and most
preferably from about 70 weight percent to about 99 weight percent.
In the preferred embodiment, the inventive composition contains
from about 1 to about 99 weight percent HCFC-241fa preferably from
about 70 weight percent to about 1 weight percent and most
preferably from about 30 weight percent to about 1 weight percent.
The composition of the present invention has a boiling point of
about from 21.degree. C. to about 60.degree. C. at a pressure from
about 16.5 psia to about 54.6 psia. An azeotropic or azeotrope-like
composition having about 98.+-.2 weight percent HF and about 2.+-.2
weight percent HCFC-241fa has been found to boil at about
21.degree. C. and 16.5 psia.
[0041] The following non-limiting examples serve to illustrate the
invention.
Example 1
[0042] 15.4 g of 1,1,3,3-tetrachloro-1-fluoropropane (HCFC-241fa)
were dissolved in 12.9 g of HF to form a heterogeneous azeotrope
mixture. This experiment was done at 21.degree. C., and at 16.5
psia.
Example 2
[0043] Binary compositions containing solely
1,1,3,3-tetrachloro-1-fluoropropane (HCFC-241fa) and HF are blended
to form a heterogeneous azeotrope mixtures at different
compositions. The vapor pressures of the mixtures are measured at
about 29.9.degree. C. and 60.degree. C. and the following results
are noticed.
[0044] Table 1 shows the vapor pressure measurement of HCFC-241fa
and HF as a function of composition of weight percent HF at
constant temperatures of about 29.9.degree. C. and 60.degree.
C.
TABLE-US-00001 TABLE 1 P-T-X of HCFC-241fa/HF System Wt. % HF T =
29.9.degree. C. T = 60.degree. C. 0.0 0.23 0.72 9.2 21.00 53.44
15.8 21.64 54.29 22.5 21.67 54.32 31.3 21.69 54.50 37.5 21.68 54.50
54.3 21.62 54.50 55.9 21.58 54.55 71.7 21.35 54.56 91.5 21.36 53.87
100.0 21.34 53.58
[0045] These data also show that the mixture is an azeotrope since
the vapor pressures of mixtures of HCFC-241fa and HF are higher, at
all indicated blend proportions, than HCFC-241fa and HF alone,
i.e., as indicated in the first and last rows when HF is 0.0 wt %
and HCFC-241fa is at 100.0 wt % as well as when HCFC-241fa is at
0.0 wt % and HF is at 100.0 wt. %. The data from Table 1 are shown
in graphic form in FIG. 1.
Example 3
[0046] The azeotropic composition of the HCFC-241fa/HF mixture is
also verified by Vapor-Liquid-Liquid Equilibrium (VLLE) experiment.
57.5 g of 1,1,3,3-tetrachloro-1-fluoropropane (HCFC-241fa) are
dissolved in 32.5 g of HF to form a heterogeneous mixture (visual
observation) at 21.degree. C. The vapor compositions of the mixture
were sampled at room temperature of 21.degree. C. The result shows
that the azeotropic composition is about 98.+-.2 wt % HF at
21.degree. C.
[0047] As used herein, the singular forms "a", "an" and "the"
include plural unless the context clearly dictates otherwise.
Moreover, when an amount, concentration, or other value or
parameter is given as either a range, preferred range, or a list of
upper preferable values and lower preferable values, this is to be
understood as specifically disclosing all ranges formed from any
pair of any upper range limit or preferred value and any lower
range limit or preferred value, regardless of whether ranges are
separately disclosed. Where a range of numerical values is recited
herein, unless otherwise stated, the range is intended to include
the endpoints thereof, and all integers and fractions within the
range. It is not intended that the scope of the invention be
limited to the specific values recited when defining a range.
[0048] It should be understood that the foregoing description is
only illustrative of the present invention. Various alternatives
and modifications can be devised by those skilled in the art
without departing from the invention. Accordingly, the present
invention is intended to embrace all such alternatives,
modifications and variances that fall within the scope of the
appended claims.
* * * * *