U.S. patent application number 13/808326 was filed with the patent office on 2013-05-02 for stable 2,3,3,3-tetrafluoropropene composition.
This patent application is currently assigned to Arkema France. The applicant listed for this patent is Beatrice Boussand. Invention is credited to Beatrice Boussand.
Application Number | 20130105724 13/808326 |
Document ID | / |
Family ID | 43569402 |
Filed Date | 2013-05-02 |
United States Patent
Application |
20130105724 |
Kind Code |
A1 |
Boussand; Beatrice |
May 2, 2013 |
STABLE 2,3,3,3-TETRAFLUOROPROPENE COMPOSITION
Abstract
The invention relates to a stable composition (CS) comprising at
least x wt.-% 2,3,3,3-tetrafluoropropene (99.8.ltoreq.x<100), at
most y wt.-% unsaturated compound(s) (Ia) (0<y.ltoreq.0.2)
selected from among 3,3,3-trifluoropropene (HFO-1243zf) and the
positional isomers of 2,3,3,3-tetrafluoropropene, such as
1,3,3,3-tetrafluoropropene (isomers Z and E) and
1,1,2,3-tetrafluoropropene, and, optionally, at most 500 ppm of
3,3,3-trifluoropropyne and/or at most 200 ppm
1,1,1,2,3-pentafluoropropene (HFO-1225ye).
Inventors: |
Boussand; Beatrice; (Sainte
Foy Les Lyon, FR) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Boussand; Beatrice |
Sainte Foy Les Lyon |
|
FR |
|
|
Assignee: |
Arkema France
Colombes
FR
|
Family ID: |
43569402 |
Appl. No.: |
13/808326 |
Filed: |
June 20, 2011 |
PCT Filed: |
June 20, 2011 |
PCT NO: |
PCT/FR2011/051406 |
371 Date: |
January 4, 2013 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
61364539 |
Jul 15, 2010 |
|
|
|
Current U.S.
Class: |
252/68 ;
570/136 |
Current CPC
Class: |
C10M 2209/043 20130101;
C10N 2030/08 20130101; C09K 5/04 20130101; C10N 2020/101 20200501;
C10N 2040/30 20130101; C10M 2207/2835 20130101; C07C 21/18
20130101; C09K 2205/126 20130101; C09K 2205/22 20130101; C10M
2209/1033 20130101; C09K 5/045 20130101; C10M 171/008 20130101;
C10M 2209/1033 20130101; C10M 2209/1095 20130101 |
Class at
Publication: |
252/68 ;
570/136 |
International
Class: |
C09K 5/04 20060101
C09K005/04 |
Foreign Application Data
Date |
Code |
Application Number |
Jul 9, 2010 |
FR |
1055628 |
Claims
1. Stable composition comprising at least about 99.8 to 100% by
weight of 2,3,3,3-tetrafluoropropene, at most about 0 to 0.2% by
weight of unsaturated compound selected from the group consisting
of 3,3,3-trifluoropropene (HFO-1243zf), the positional isomers of
2,3,3,3-tetrafluoropropene, 1,1,2,3-tetrafluoropropene, and
mixtures thereof.
2. Stable composition according to claim 1, characterized in that
it further comprises at least one compound selected from the group
consisting of 1,1,1,2-tetrafluoropropane (HFC-254eb),
1,1,1,2,3-pentafluoropropane (HFC-245eb), 1,1,1,2-tetrafluoroethane
(HFC-134a), 1,1,2-trifluoroethane (HFC-143),
1,1,1,2,3,3-hexafluoropropane, hexafluoropropene,
cyclohexafluoropropene, 1,1,1,3,3-pentafluoropropene (HFO-1225zc)
and mixtures thereof.
3. Stable composition according to claim 2, characterized in that
the compound comprises at most 500 ppm of the stable
composition.
4. Stable composition according to claim 1, characterized in that
it comprises at least 99.85% by weight of
2,3,3,3-tetrafluoropropene, at most about 0 to 0.15% by weight of
unsaturated compound selected from the group consisting of
3,3,3-trifluoropropene (HFO-1243zf), the positional isomers of
2,3,3,3-tetrafluoropropene, 1,1,2,3-tetrafluoropropene, and
mixtures thereof.
5. Stable composition according to claim 1, characterized in that
it comprises at least 99.9% by weight of
2,3,3,3-tetrafluoropropene, at most about 0 to 0.1% by weight of
unsaturated compound selected from the group consisting of
3,3,3-trifluoropropene (HFO-1243zf), the positional isomers of
2,3,3,3-tetrafluoropropene, 1,1,2,3-tetrafluoropropene, and
mixtures thereof.
6. Stable composition according to claim 1, characterized in that
it comprises from 99.85 to 99.98% by weight of
2,3,3,3-tetrafluoropropene, from 0.02 to 0.15% by weight of
unsaturated compound(s) (Ia) chosen from 3,3,3-trifluoropropene
(HFO-1243zf) and the positional isomers of
2,3,3,3-tetrafluoropropene, such as 1,3,3,3-tetrafluoropropene (Z
and E isomers) and 1,1,2,3-tetrafluoropropene, and optionally at
most 200 ppm of 3,3,3-trifluoropropyne and/or at most 5 ppm of
1,1,1,2,3-pentafluoropropene (HFO-1225ye) and/or at most 400 ppm of
compounds (Ib).
7. (canceled)
8. Stable composition according to claim 1, characterized in that
it further comprises a lubricant.
9. Stable composition according to claim 8, characterized in that
the lubricant is selected from the group consisting of polyol
esters (POEs), polyalkylene glycols (PAGs), polyalkylene glycol
esters, polyvinyl ethers (PVEs) and mixtures thereof.
10. 2,3,3,3-Tetrafluoropropene which has a purity of greater than
or equal to 99.8% by weight and less than 100% by weight and which
comprises at most 0.2% by weight of unsaturated compound selected
from the group consisting of 3,3,3-trifluoropropene (HFO-1243zf),
the positional isomers of 2,3,3,3-tetrafluoropropene,
1,1,2,3-tetrafluoropropene, and mixtures thereof.
11. 2,3,3,3-Tetrafluoropropene according to claim 10, characterized
by a purity of greater than or equal to 99.9% by weight and less
than 100% by weight and comprising at most 0.1% by weight of
unsaturated compound selected from the group consisting of
3,3,3-trifluoropropene (HFO-1243zf), the positional isomers of
2,3,3,3-tetrafluoropropene, 1,1,2,3-tetrafluoropropene, and
mixtures thereof.
12. Stable composition according to claim 1, characterized in that
it further comprises up to about 500 ppm of
3,3,-trifluoropropyne.
13. Stable composition according to claim 1, characterized in that
it further comprises up to about 200 ppm of
1,1,1,2,3-pentafluoropropene (HFO-1225ye).
14. Stable composition according to claim 4, characterized in that
it further comprises up to about 250 ppm of
3,3,3,-trifluoropropyne.
15. Stable composition according to claim 4, characterized in that
it further comprises up to about 50 ppm of
1,1,1,2,3-pentafluoropropene (HFO-1225ye).
16. Stable composition according to claim 5, characterized in that
further comprises up to about 200 ppm of
3,3,3,-trifluoropropyne.
17. Stable composition according to claim 5, characterized in that
it further comprises up to about 5 ppm of
1,1,1,2,3-pentafluoropropene (HFO-1225ye).
18. Stable composition according to claim 10, characterized in that
it further comprises up to about 500 ppm of
3,3,3,-trifluoropropyne.
19. Stable composition according to claim 10, characterized in that
it further comprises up to about 200 ppm of
1,1,1,2,3-pentafluoropropene (HFO-1225ye).
20. Stable composition according to claim 10, characterized in that
it further comprises up to about 500 ppm of a compound selected
from the group consisting of 1,1,1,2-tetrafluoropropane
(HFC-254eb), 1,1,1,2,3-pentafluoropropane (HFC-245eb),
1,1,1,2-tetrafluoroethane (HFC-134a), 1,1,2-trifluoroethane
(HFC-143), 1,1,1,2,3,3-hexafluoropropane, hexafluoropropene,
cyclohexafluoropropene, 1,1,1,3,3-pentafluoropropene (HFO-1225zc)
and mixtures thereof.
21. Stable composition according to claim 11, characterized in that
it further comprises up to about 200 ppm of
3,3,3,-trifluoropropyne.
22. Stable composition according to claim 11, characterized in that
it funder comprises up to about 5 ppm of
1,1,1,2,3-pentafluoropropene.
23. Stable composition according to claim 11, characterized in that
it further comprises up to about 500 ppm of a compound selected
from the group consisting of 1,1,1,2-tetrafluoropropane
(HFC-254eb), 1,1,1,2,3-pentafluoropropane (HFC-245eb),
1,1,1,2-tetrafluoroethane (HFC-134a), 1,1,2-trifluoroethane
(HFC-143), 1,1,1,2,3,3-hexafluoropropane, hexafluoropropene,
cyclohexafluoropropene, 1,1,1,3,3-pentafluoropropene (HFO-1225zc)
and mixtures thereof.
Description
[0001] The present invention relates to a stable composition
including 2,3,3,3-tetrafluoropropene capable of being used in
refrigeration and air conditioning.
[0002] The problems presented by substances which deplete the
atmospheric ozone layer were dealt with at Montreal, where the
protocol was signed imposing a reduction on the production and use
of chlorofluorocarbons (CFCs). This protocol has formed the subject
of amendments which have required the abandoning of CFCs and have
extended regulation to other products, including
hydrochlorofluorocarbons (HCFCs).
The refrigeration and air conditioning industries have invested a
great deal in the replacement of these refrigerants and it is
because of this that hydrofluorocarbons (HFCs) have been
marketed.
[0003] In the motor vehicle industry, the air conditioning systems
of commercial vehicles have been changed in many countries from a
refrigerant comprising chlorofluorocarbon (CFC-12) to that of
hydrofluorocarbon (1,1,1,2-tetrafluoroethane: HFC-134a), which is
less harmful to the ozone layer. However, from the viewpoint of the
objectives set by the Kyoto protocol, HFC-134a (GWP=1430) is
regarded as having a high heating power. The contribution to the
greenhouse effect of a refrigerant is quantified by a criterion,
the GWP (Global Warning Potential), which summarizes the heating
power by taking a reference value of 1 for carbon dioxide.
[0004] Hydrofluoroolefins (HFOs) have a low heating power and thus
meet the objectives set by the Kyoto protocol. The document JP
4-110388 discloses 2,3,3,3-tetrafluoropropene (HFO-1234yf) as heat
transfer agent in refrigeration, air conditioning and heat
pumps.
[0005] In addition to having good properties as a heat transfer
agent, in order for a refrigerant to be accepted commercially, it
must in particular be thermally stable and be compatible with
lubricants. This is because it is highly desirable for the
refrigerant to be compatible with a lubricant used in the
compressor present in the majority of refrigeration systems. This
refrigerant and lubricant combination is important for the use and
the effectiveness of the refrigeration system; in particular, the
lubricant has to be sufficiently soluble in the refrigerant
throughout the operating temperature range.
[0006] According to the document WO 2008/042066, as fluoroolefins
are capable of decomposing on contact with moisture, oxygen or
other compounds when they are used as refrigerant, possibly at high
temperature, it is recommended to stabilize them with at least one
amine.
[0007] Other stabilizing agents, such as benzophenone derivatives,
lactones and some phosphorus-comprising compounds, have also been
proposed for stabilizing fluoroolefins (WO 2008/027596, WO
2008/027516 and WO 2008/027515).
[0008] Furthermore, the document EP 2 149 543 describes a process
for the purification of 1,1,1,2,3-pentafluoropropane, a starting
material in the manufacture of HFO-1234yf, in order to obtain a
product having a 1,1,1,2,3-pentafluoropropene (HFO-1225ye) content
of less than 500 ppm and a trifluoropropyne content of less than 50
ppm.
[0009] The Applicant Company has now developed a
2,3,3,3-tetrafluoropropene composition which makes it possible to
improve the thermal stability when it is used in refrigeration
systems.
[0010] A subject-matter of the present invention is thus a stable
composition (SC) comprising at least x% by weight of
2,3,3,3-tetrafluoropropene (99.8.ltoreq.x<100), at most y% by
weight of unsaturated compound(s) (Ia) (0<y.ltoreq.0.2) chosen
from 3,3,3-trifluoropropene (HFO-1243zf) and the positional isomers
of 2,3,3,3-tetrafluoropropene, such as 1,3,3,3-tetrafluoropropene
(Z and E isomers) and 1,1,2,3-tetrafluoropropene, and optionally at
most 500 ppm of 3,3,3-trifluoropropyne and/or at most 200 ppm of
1,1,1,2,3-pentafluoropropene (HFO-1225ye).
[0011] The stable composition according to the present invention
can additionally comprise at least one of the compounds (Ib) chosen
from 1,1,1,2-tetrafluoropropane (HFC-254eb),
1,1,1,2,3-pentafluoropropane (HFC-245eb), 1,1,1,2-tetrafluoroethane
(HFC-134a), 1,1,2-trifluoroethane (HFC-143),
1,1,1,2,3,3-hexafluoropropane, hexafluoropropene,
cyclohexafluoropropene and 1,1,1,3,3-pentafluoropropene
(HFO-1225zc).
[0012] The combined compounds (Ib) present in the composition
according to the present invention represent at most 500 ppm.
[0013] Preferably, the SC composition comprises at least 99.85% by
weight of 2,3,3,3-tetrafluoropropene, at most y% by weight of
unsaturated compound(s) (Ia) (0<y.ltoreq.0.15) chosen from
3,3,3-trifluoropropene (HFO-1243zf) and the positional isomers of
2,3,3,3-tetrafluoropropene, such as 1,3,3,3-tetrafluoropropene (Z
and E isomers) and 1,1,2,3-tetrafluoropropene, and optionally at
most 250 ppm of 3,3,3-trifluoropropyne and/or at most 50 ppm of
1,1,1,2,3-pentafluoropropene (HFO-1225ye).
[0014] The SC composition which is particularly preferred comprises
at least 99.9% by weight of 2,3,3,3-tetrafluoropropene, at most y%
by weight of unsaturated compound(s) (Ia) (0<y.ltoreq.0.1)
chosen from 3,3,3-trifluoropropene (HFO-1243zf) and the positional
isomers of 2,3,3,3-tetrafluoropropene, such as
1,3,3,3-tetrafluoropropene (Z and E isomers) and
1,1,2,3-tetrafluoropropene, and optionally at most 200 ppm of
3,3,3-trifluoropropyne and/or at most 5 ppm of
1,1,1,2,3-pentafluoropropene (HFO-1225ye).
[0015] According to a preferred embodiment of the invention, the SC
composition comprises from 99.85 to 99.98% by weight of
2,3,3,3-tetrafluoropropene, from 0.02 to 0.15% by weight of
unsaturated compound(s) (Ia) chosen from 3,3,3-trifluoropropene
(HFO-1243zf) and the positional isomers of
2,3,3,3-tetrafluoropropene, such as 1,3,3,3-tetrafluoropropene (Z
and E isomers) and 1,1,2,3-tetrafluoropropene, and optionally at
most 200 ppm of 3,3,3-trifluoropropyne and/or at most 5 ppm of
1,1,1,2,3-pentafluoropropene (HFO-1225ye) and/or at most 400 ppm of
compounds (Ib).
[0016] The stable composition according to the invention exhibits
the advantage of being able to be obtained directly by a process
for the manufacture of 2,3,3,3-tetrafluoropropene, optionally after
at least one separation stage.
[0017] Another subject-matter of the present invention is
2,3,3,3-tetrafluoropropene which has a purity of greater than or
equal to 99.8% by weight and less than 100% by weight and which
comprises at most 0.2% by weight of unsaturated compounds (Ia),
optionally at most 500 ppm of 3,3,3-trifluoropropyne and/or at most
200 ppm of 1,1,1,2,3-pentafluoropropene and/or at most 500 ppm of
compounds (Ib).
[0018] An additional subject-matter of the present invention is
2,3,3,3-tetrafluoropropene which has a purity of greater than or
equal to 99.9% by weight and less than 100% by weight and which
comprises at most 0.1% by weight of unsaturated compounds (Ia),
optionally at most 200 ppm of 3,3,3-trifluoropropyne and/or at most
5 ppm of 1,1,1,2,3-pentafluoropropene and/or at most 500 ppm of
compounds (Ib).
[0019] 2,3,3,3-Tetrafluoropropene can be obtained from
hexafluoropropene (HFP) in at least 4 reaction stages: -(i)
hydrogenation of HFP in the presence of a hydrogenation catalyst in
a solid phase to give 1,1,1,2,3,3-hexafluoropropane; (ii)
dehydrofluorination of the 1,1,1,2,3,3-hexafluoropropane obtained
in stage (i) in the liquid phase using an alkali metal hydroxide or
in the gas phase in the presence of a dehydrohalogenation catalyst
to give 1,1,1,2,3-pentafluoropropene; (iii) hydrogenation of the
HFO-1225ye obtained in (ii) in the presence of a hydrogenation
catalyst in the solid phase to give 1,1,1,2,3-pentafluoropropane;
(iv) dehydrofluorination of the HFC-245eb obtained in stage (iii)
in the liquid phase using an alkali metal hydroxide or in the gas
phase in the presence of a dehydrohalogenation catalyst to give
2,3,3,3-tetrafluoropropene.
[0020] 2,3,3,3-Tetrafluoropropene can be obtained from
hexafluoropropene (HFP) in at least 2 reaction stages: -(i)
hydrogenation of HFP in the presence of a hydrogenation catalyst in
the solid phase to give 1,1,1,2,3-pentafluoropropane; (ii)
dehydrofluorination of the HFC-245eb obtained in stage (i) in the
liquid phase using an alkali metal hydroxide or in the gas phase in
the presence of a dehydrohalogenation catalyst to give
2,3,3,3-tetrafluoropropene.
[0021] The 2,3,3,3-tetrafluoropropene according to the present
invention can be obtained from HFP according to a process as
described above after a purification of the HFC-245eb and/or after
purification of the 2,3,3,3-tetrafluoropropene
Thus, the HFC-245eb, prior to the dehydrofluorination stage, is,
for example, purified by distillation at an absolute pressure of 6
bar and at a column bottom temperature of 80.degree. C. and a top
temperature of 50.degree. C. with approximately 30 theoretical
plates and a reflux ratio of approximately 37.
[0022] After the final dehydrofluorination stage, the HFO-1234yf is
subjected to double distillation. The first distillation is carried
out at an absolute pressure of approximately 13 bar, a column
bottom temperature of approximately 60.degree. C. and a top
temperature of approximately 40.degree. C. and with approximately
35 theoretical plates and a reflux ratio of approximately 500. The
second distillation is carried out at an absolute pressure of
approximately 11 bar, a column bottom temperature of approximately
105.degree. C., and a top temperature of approximately 44.degree.
C. and with approximately 30 theoretical plates at a reflux ratio
of approximately 4.
[0023] The 2,3,3,3-tetrafluoropropene can also be obtained from
1,1,1-trifluoro-2-chloropropene by hydrofluorination in the liquid
or gas phase in the presence of a fluorination catalyst. The
2,3,3,3-tetrafluoropropene thus obtained can be purified to give
the 2,3,3,3-tetrafluoropropene according to the present
invention.
[0024] The compositions according to the present invention are
capable of being used as heat transfer agent in stationary or
motor-vehicle air conditioning, refrigeration and heat pumps.
[0025] Another subject-matter of the present invention is the
compositions as described above in combination with a
lubricant.
[0026] Mention may in particular be made, as lubricant, of polyol
esters (POEs), polyalkylene glycols (PAGs), polyalkylene glycol
esters and polyvinyl ethers (PVEs).
[0027] The PAG lubricants are in the oxyalkylene homo- or copolymer
form. The preferred PAGs are homopolymers composed of oxypropylene
groups with a viscosity of 10 to 200 centistokes at 40.degree. C.,
advantageously between 30 and 80 centistokes. The hydroxyl groups
at the ends of the oxyalkylene homo- or copolymer chains can be
more or less replaced by --O--C.sub.nH.sub.2n+1 groups where n=1 to
10; the group with n=1 being preferred. The PAGs which may be
suitable are those having hydroxyl groups for each ending or
--O--C.sub.nH.sub.2n+1 groups.
[0028] Mention may in particular be made, as POEs, of esters of
carboxylic acids having a linear or branched carbon chain of 2 to
15 atoms and of polyols having a neopentyl backbone, such as
neopentyl glycol, trimethylolpropane, pentaerythritol and
dipentaerythritol; pentaerythritol is the preferred polyol. Esters
of carboxylic acids having a carbon chain of 4 to 9 atoms are
preferred.
[0029] Mention may in particular be made, as carboxylic acid of 4
to 9 carbon atoms, of n-pentanoic acid, n-hexanoic acid,
n-heptanoic acid, n-octanoic acid, 2-ethylhexanoic acid,
2,2-dimethylpentanoic acid, 3,5,5-trimethylhexanoic acid, adipic
acid and succinic acid.
[0030] Some alcohol functional groups are not esterified; however,
the proportion remains low.
[0031] The POE oils selected can comprise between 0 and 5 relative
mol % of CH.sub.2--O units with respect to the
--CH.sub.2--O--(C.dbd.O)-- units.
The preferred POE lubricants are those having a viscosity of 1 to
1000 centistokes (cSt) at 40.degree. C., preferably of 10 to 200
cSt and advantageously of 30 to 80 cSt
EXPERIMENTAL PART
[0032] The thermal stability trials are carried out according to
Standard ASHRAE 97-2007: "sealed glass tube method to test the
chemical stability of materials for use within refrigerant
systems".
The test conditions are as follows: Weight of fluid: 2.2 g Weight
of lubricant: 5 g
Temperature: 200.degree. C.
[0033] Duration: 14 days
[0034] Lengths of steel are introduced into tubes.
The length of steel and the lubricant are introduced into a 42.2 ml
glass tube. The tube is subsequently evacuated under vacuum and
then the fluid F is added thereto. The tube is then welded in order
to close it and placed in an oven at 200.degree. C. for 14
days.
[0035] At the end of the test, various analyses are carried out:
[0036] the gas phase is recovered in order to be analysed by gas
chromatography: the main impurities were identified by GC/MS
(coupled gas chromatography/mass spectrometry). The impurities
coming from the fluid F and those coming from the lubricant can
thus be combined. [0037] the length of steel is weighed
(measurement of the rate of corrosion) and observed under a
microscope. [0038] the lubricant is analysed: colour (by
spectrocolorimetry, Labomat DR Lange LICO220 model MLG131), water
content (by Karl Fischer coulornetry, Mettler DL37) and acid number
(by quantitative determination with 0.01N methanolic potassium
hydroxide).
[0039] The lubricant used in the tests is a commercial PAG oil: PAG
ND8.
The fluid used for these trials comprises essentially HFO-1234yf
(at least 99.9% by weight) and then 300 ppm of HFO-1243zf, 500 ppm
of E HFO-1234ze and 300 ppm of HFO-1243zf+500 ppm of E HFO-1234ze
are respectively added to the fluid.
TABLE-US-00001 Content of ppm ppm ppm ppm E HFO-1234ze -- -- 500
500 added HFO-1243zf -- 300 300 added Byproducts in the gas phase:
from the 600 ppm 600 ppm 900 ppm 900 ppm HFO-1234yf from the oil
1.4% 1.4% 1.4% 1.4% Rate of <5 .mu.m/year <5 .mu.m/year <5
.mu.m/year <5 .mu.m/year corrosion Analysis of the oil: colour
10 Gardner 9 Gardner 8.5 Gardner 9 Gardner water content 300 ppm
300 ppm 250 ppm 300 ppm acid number 5.2 mg 5.2 mg 4.5 mg 5.2 mg
KOH/g KOH/g KOH/g KOH/g
[0040] The examples show that the presence of the compounds (Ia) is
not harmful to the thermal stability, either of the HFO-1234yf
composition or of the lubricant, and in some cases improves it.
* * * * *