U.S. patent application number 16/545294 was filed with the patent office on 2019-12-12 for compositions based on 1,1,3,3-tetrachloropropene.
This patent application is currently assigned to ARKEMA FRANCE. The applicant listed for this patent is ARKEMA FRANCE. Invention is credited to Bertrand COLLIER, Anne PIGAMO.
Application Number | 20190375698 16/545294 |
Document ID | / |
Family ID | 53758425 |
Filed Date | 2019-12-12 |
United States Patent
Application |
20190375698 |
Kind Code |
A1 |
PIGAMO; Anne ; et
al. |
December 12, 2019 |
COMPOSITIONS BASED ON 1,1,3,3-TETRACHLOROPROPENE
Abstract
Compositions based on F-1230za (1,1,3,3-tetrachloropropene), or
on a mixture consisting of F-1230za and F-1230zd
(1,3,3,3-tetrachloropropene), the manufacture thereof, and also the
use thereof in particular for the production of F-1233zdE
(trans-1-chloro-3,3,3-trifluoropropene), F-1234zeE
(trans-1,3,3,3-tetrafluoropropene), and/or F-245fa
(1,1,1,3,3-pentafluoropropane). A process for manufacturing the
composition, the process including the following steps: reaction of
carbon tetrachloride with ethylene to produce
1,1,1,3-tetrachloropropane (F-250fb); chlorination of F-250fb to
obtain 1,1,1,3,3-pentachloropropane (F-240fa); dehydrochlorination
of F-240fa to obtain 1,1,3,3-tetrachloropropene (F-1230za); one or
more steps for separating out the F-1230za.
Inventors: |
PIGAMO; Anne; (Francheville,
FR) ; COLLIER; Bertrand; (Saint-Genis-Laval,
FR) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
ARKEMA FRANCE |
Colombes |
|
FR |
|
|
Assignee: |
ARKEMA FRANCE
Colombes
FR
|
Family ID: |
53758425 |
Appl. No.: |
16/545294 |
Filed: |
August 20, 2019 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
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15575980 |
Nov 21, 2017 |
10427998 |
|
|
PCT/FR2016/051054 |
May 4, 2016 |
|
|
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16545294 |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C07C 17/206 20130101;
C07C 17/38 20130101; C07C 17/25 20130101; C07C 17/383 20130101;
C09K 5/045 20130101; C07C 17/383 20130101; C07C 17/38 20130101;
C09K 2205/126 20130101; C07C 17/087 20130101; C09K 2205/24
20130101; C07C 17/206 20130101; C09K 5/044 20130101; C07C 17/10
20130101; C07C 17/206 20130101; C07C 17/266 20130101; C07C 17/266
20130101; C07C 17/25 20130101; C07C 17/093 20130101; C07C 19/01
20130101; C07C 17/206 20130101; C07C 17/206 20130101; C07C 17/269
20130101; C07C 17/25 20130101; C07C 17/38 20130101; C07C 21/04
20130101; C07C 21/18 20130101; C07C 21/04 20130101; C07C 19/10
20130101; C07C 21/18 20130101; C07C 17/383 20130101; C07C 17/25
20130101; C07C 21/04 20130101; C07C 17/269 20130101; C07C 21/18
20130101; C07C 19/08 20130101; C07C 19/01 20130101; C07C 21/04
20130101; C07C 19/01 20130101; C07C 21/04 20130101; C07C 19/08
20130101; C07C 19/10 20130101; C07C 19/08 20130101 |
International
Class: |
C07C 17/20 20060101
C07C017/20; C07C 17/269 20060101 C07C017/269; C07C 17/266 20060101
C07C017/266; C07C 17/093 20060101 C07C017/093; C09K 5/04 20060101
C09K005/04 |
Foreign Application Data
Date |
Code |
Application Number |
May 22, 2015 |
FR |
1554655 |
Claims
1. A composition comprising at least 99.5% by weight of
1,1,3,3-tetrachloropropene (F-1230za), or a mixture of
1,1,3,3-tetrachloropropene and of 1,3,3,3-tetrachloropropene
(F-1230zd), and at least one additional compound chosen from a list
of compounds consisting of pentachloropropanes, tetrachloropropenes
other than F-1230za and F-1230zd, chlorobutenes, chlorobutanes and
oxygenated compounds, said compound and/or the total amount of said
compounds being present in the composition in a content of less
than or equal to 0.5% by weight.
2. The composition as claimed in claim 1, in which said additional
compound represents a content of less than or equal to 1000 ppm; or
less than or equal to 500 ppm; or less than or equal to 450 ppm; or
less than or equal to 400 ppm; or less than or equal to 350 ppm; or
less than or equal to 300 ppm; or less than or equal to 250 ppm; or
less than or equal to 200 ppm; or less than or equal to 150 ppm; or
less than or equal to 100 ppm; or less than or equal to 75 ppm; or
less than or equal to 50 ppm; or less than or equal to 25 ppm; or
less than or equal to 10 ppm; or less than or equal to 5 ppm, in
the composition.
3. The composition as claimed in claim 2, in which said additional
compound is or are chosen from 1,1,1,3,3-pentachloropropane
(F-240fa), 1,1,1,2,3-pentachloropropane (F-240db) and
1,1,2,3-tetrachloropropene (F-1230xa).
4. A process for manufacturing the composition as claimed in claim
1, comprising the following steps: reaction of carbon tetrachloride
with vinyl chloride to produce 1,1,1,3,3-pentachloropropane
(F-240fa); dehydrochlorination of F-240fa to obtain
1,1,3,3-tetrachloropropene (F-1230za); one or more steps for
separating out the F-1230za.
5. A process for manufacturing the composition as claimed in claim
1, comprising the following steps: reaction of carbon tetrachloride
with ethylene to produce 1,1,1,3-tetrachloropropane (F-250fb);
chlorination of F-250fb to obtain 1,1,1,3,3-pentachloropropane
(F-240fa); dehydrochlorination of F-240fa to obtain
1,1,3,3-tetrachloropropene (F-1230za); one or more steps for
separating out the F-1230za.
6. The process as claimed in claim 4, in which the separation is
performed by distillation or extraction, and/or by physicochemical
separation on molecular sieves, alumina or active charcoal, and/or
by membrane separation, optionally in the gas phase.
7. The process as claimed in claim 6, in which a first separation
step is performed via one or more distillations and a second
separation step is performed by adsorption on molecular sieves, on
active charcoal or on a mixture thereof.
8. The process as claimed in claim 6, in which the separation step
is performed by adsorption on zeolite, of the type such as 4A, 5A,
10.times. or 13.times. molecular sieves, and optionally followed by
gas-phase membrane separation.
9. The process as claimed in claim 6, in which the step of
separation by adsorption is performed at a temperature of between 0
and 120.degree. C. and preferably between 20 and 80.degree. C.
10. The use of the composition as claimed in claim 1 in the
manufacture of 1-chloro-3,3,3-trifluoropropene (F-1233zd),
1,3,3,3-tetrafluoropropene (F-1234ze) or
1,1,1,3,3-pentafluoropropane (F-245fa).
11. A process for manufacturing 1-chloro-3,3,3-trifluoropropene
(F-1233zd), and/or 1,3,3,3-tetrafluoropropene (F-1234ze) and/or
1,1,1,3,3-pentafluoropropane (F-245fa), by fluorination performed
in the liquid phase and in the absence of catalyst, comprising the
steps: of introducing into a fluorination reactor a stream
comprising the composition as in claim 1.
12. The process as claimed in claim 11 for forming
trans-1-chloro-3,3,3-trifluoropropene (F-1233zdE) or
trans-1,3,3,3-tetrafluoropropene (F-1234zeE).
13. The process as claimed in claim 11, followed by one or more
steps for separating 1-chloro-3,3,3-trifluoropropene (F-1233zd),
and/or 1,3,3,3-tetrafluoropropene (F-1234ze) and/or
1,1,1,3,3-pentafluoropropane (F-245fa) from the stream of products.
Description
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] The present application is a continuation of U.S.
application Ser. No. 15/575,980, filed on Nov. 21, 2017, which is a
U.S. national stage of International Application No.
PCT/FR2016/051054, filed on May 4, 2016, which claims the benefit
of French Application No. 1554655, filed on 22 May 2015. The entire
contents of each of U.S. application Ser. No. 15/575,980,
International Application No. PCT/FR2016/051054, and French
Application No. 1554655 are hereby incorporated herein by reference
in their entirety.
FIELD OF THE INVENTION
[0002] The present invention relates to compositions based on
F-1230za (1,1,3,3-tetrachloropropene), or a mixture consisting of
F-1230za and F-1230zd (1,3,3,3-tetrachloropropene), to the
manufacture thereof, and also to the use thereof especially for the
production of F-1233zdE (trans-1-chloro-3,3,3-trifluoropropene),
F-1234zeE (trans-1,3,3,3-tetrafluoropropene) and/or F-245fa
(1,1,1,3,3-pentafluoropropane).
TECHNICAL BACKGROUND
[0003] Fluoroolefins, and in particular F-1233zdE, are compounds of
major interest for refrigeration and air-conditioning systems,
given the new environmental regulations.
[0004] It is known practice to produce hydrofluoroolefins such as
F-1233zdE by fluorination of hydrochloroolefins or
chlorohydrocarbons in particular. This fluorination is generally a
fluorination using hydrofluoric acid as fluorinating agent.
[0005] Among the routes for obtaining F-1233zdE, it is in
particular known practice to use F-240fa
(1,1,1,3,3-pentachloropropane) as starting compound. Reference is
made, for example, to U.S. Pat. No. 8,704,017 in this regard, which
describes a process of liquid-phase fluorination in the absence of
catalyst but requiring several reactors in series and/or stirring
of the reaction medium to counter the low degree of conversion.
[0006] US 2014/0221704 teaches the low miscibility between F-240fa
and hydrogen fluoride, and proposes the addition of a
phase-transfer agent to the reaction medium to solve this
problem.
[0007] US 2013/0211154 suggests increasing the pressure in the
reaction medium to improve the degree of conversion of F-240fa.
[0008] Another possible process is the liquid-phase fluorination of
F-1230za, in the absence of catalyst and under much less severe
conditions, this olefinic starting material not having these
difficulties of low degree of conversion.
[0009] However, it is known that a liquid-phase fluorination
process may generate several undesired compounds such as oligomeric
compounds, products of high boiling point, toxic or corrosive
compounds, or, more generally, impurities that are difficult to
separate out. In particular, these oligomeric compounds have the
consequence of reducing the efficiency of the fluorination process
and must be separated out by a purge, in a continuous system or in
a batch system, obtained from the reactor and retreated. Compounds
of high boiling point may also prevent the reaction.
[0010] The harmful effects of impurities on fluorination processes
were also observed in the abovementioned reaction of F-1230za.
[0011] Stabilization of tetrachloropropenes with inhibitors,
generally antioxidants, is taught in US 2012/0226081, US
2012/0190902 or US 2014/0213831. These inhibitors prevent the
formation of oxygenated impurities, mainly phosgene which is toxic,
during the phases of transportation and storage. However, the
impact of these impurities in a liquid-phase fluorination process
is not described.
[0012] It is desirable to be able to produce F-1233zdE under good
yield conditions on an industrial scale using a process that is
simple to perform, especially in the liquid phase and in the
absence of catalyst, which allows an improvement in the yield
and/or which does not present any difficulties in terms of
separating out undesired compounds.
SUMMARY OF THE INVENTION
[0013] The invention is based on the surprising discovery that when
the starting material does not contain any specific impurities, or
contains only very little thereof, the fluorination in the absence
of catalyst of F-1230za, or of F-1230za mixed with F-1230zd, is
markedly more efficient. The product stream is richer in F-1233zdE
and contains fewer undesired compounds.
[0014] The invention relates firstly to a composition comprising at
least 99.5% by weight of 1,1,3,3-tetrachloropropene or a mixture of
1,1,3,3-tetrachloropropene and of 1,3,3,3-tetrachloropropene, and
comprising at least one compound chosen from a list of additional
compounds consisting of pentachloropropanes (especially F-240fa),
tetrachloropropenes other than F-1230za and F-1230zd (especially
1,1,2,3-tetrachloroprene (F-1230xa), chlorobutenes, chlorobutanes
and oxygenated compounds (for example acids, esters, aldehydes or
oxychlorides), said compound or the total amount of said compounds
being present in the composition in a weight content of less than
or equal to 0.5%.
[0015] In one embodiment, said additional compound is present in
the composition in a weight content of less than or equal to 1000
ppm and the total amount of said compounds is less than or equal to
0.5%.
[0016] According to one embodiment, the composition comprises at
least 99.5% by weight, preferably at least 99.7% by weight and
particularly preferably at least 99.8% by weight of F-1230za, or of
a mixture of F-1230za and of F-1230zd.
[0017] Secondly, the invention relates to a process for obtaining
the composition as defined above.
[0018] Next, the invention relates generally to the use of said
composition in the preparation of F-1233zd, and provides a
particular process for producing 1-chloro-3,3,3-trifluoropropene,
especially in trans form, comprising: [0019] the provision of a
composition as defined above; [0020] the reaction of this
composition with hydrofluoric acid.
[0021] Use may also be made of F-1230zd or else a mixture
constituted of F-1230za and of F-1230zd as starting reagent.
[0022] According to the preferred embodiment, the process comprises
a single fluorination step in the liquid phase and in the absence
of catalyst.
[0023] In the course of the fluorination reaction(s), some of the
impurities of the F-1230za may be converted into different
impurities in the liquid reaction medium worked under standard
temperature and pressure conditions and may accumulate in the
reactor. These oligomers are harmful to the reactivity since they
occupy the volume of the reactor and deteriorate the reaction
yield. They may also be constituted of compounds which have a
certain toxicity, or corrosiveness, which entails difficulties
during their handling for destruction. They must thus be removed by
means of a purge system before being treated and the final residue
removed.
[0024] The present invention makes it possible to overcome the
drawbacks of the prior art. The invention more particularly
provides compositions based on F-1230za of which the content of
specific impurities is controlled, making it possible to minimize
the generation of harmful oligomers in the reaction medium of the
process for manufacturing F-1233zdE.
DESCRIPTION OF EMBODIMENTS OF THE INVENTION
[0025] The invention is now described in greater detail and in a
nonlimiting manner in the description which follows.
[0026] All the contents indicated are weight contents, unless
otherwise mentioned.
Compositions According to the Invention
[0027] The invention proposes compositions based on F-1230za or a
mixture of F-1230za and F-1230zd. The content of F-1230za or the
sum of the contents of F-1230za and F-1230zd is greater than or
equal to 99.5%.
[0028] According to certain embodiments, it is greater than or
equal to 99.6%, or 99.7%, or 99.8%, or 99.9%, or 99.95%.
[0029] The compositions according to the invention also comprise at
least one compound chosen from a list of additional compounds
constituted by pentachloropropanes (especially
1,1,1,3,3-pentachloropropane or F-240fa), tetrachloropropenes
(especially 1,1,2,3-tetrachloropropene or F-1230xa), chlorobutenes,
chlorobutanes and oxygenated compounds, said compound being present
in the composition in a content of less than or equal to 0.5% by
weight; or less than or equal to 1000 ppm; or less than or equal to
500 ppm; or less than or equal to 450 ppm; or less than or equal to
400 ppm; or less than or equal to 350 ppm; or less than or equal to
300 ppm; or less than or equal to 250 ppm; or less than or equal to
200 ppm; or less than or equal to 150 ppm; or less than or equal to
100 ppm; or less than or equal to 75 ppm; or less than or equal to
50 ppm; or less than or equal to 25 ppm; or less than or equal to
10 ppm; or less than or equal to 5 ppm.
[0030] The term "oxygenated compound" refers to any compound
containing an oxygen heteroatom, such as acids, esters, aldehydes
or oxychlorides, for instance phosgene.
[0031] Particularly undesirable impurities mixed in the reaction
medium are: [0032] molecules of the F-240 series, such as F-240fa
(1,1,1,3,3-pentachloropropane), F-240da
(1,1,2,3,3-pentachloropropane), F-240db
(1,1,1,2,3-pentachloropropane), F-240ab
(1,1,1,2,2-pentachloropropane), and more particularly F-240db and
F-240fa; [0033] molecules of the F-1230 series, other than F-1230za
and F-1230zd, such as F-1230xa (1,1,2,3-tetrachloropropene),
F-1230xd (1,2,3,3-tetrachloropropene), F-1230xf
(2,3,3,3-tetrachloropropene), and more particularly the
abovementioned F-1230xa.
[0034] The molecules F-240fa, F-240db and F-1230xa are chlorinated
impurities which have undesired behaviour in the reaction medium in
the presence of HF and in the absence of catalyst. F-240fa has a
low degree of conversion and has a certain stability in the
reaction medium. It may lead to sparingly fluorinated compounds
such as F-241fa (1,1,3,3-tetrachloro-1-fluoropropane) with a high
boiling point. They have a tendency to encumber the volume of the
reaction medium without reacting sufficiently. The case is
substantially the same for F-240db. On the other hand, the molecule
F-1230xa generates a large amount of oligomers when it is heated in
the presence of HF and in the absence of catalyst.
[0035] Consequently, it is desirable to adjust the compositions
according to the invention so as to limit the presence of these
chlorinated impurities.
[0036] Thus, advantageous compositions according to the invention:
[0037] comprise at least one compound from among those of the F-240
series in a content of less than or equal to 0.5%; or less than or
equal to 1000 ppm; or less than or equal to 250 ppm; or from 150 to
200 ppm; or from 100 to 150 ppm; or from 50 to 100 ppm; or from 25
to 50 ppm; or from 10 to 25 ppm; or from 5 to 10 ppm; or less than
or equal to 5 ppm, and, for example, from 1 to 5 ppm; and/or [0038]
comprise at least one compound from among those of the F-1230
series, other than F-1230za and F-1230zd, in a content of less than
or equal to 0.5%; or less than or equal to 1000 ppm; or less than
or equal to 250 ppm; or from 150 to 200 ppm; or from 100 to 150
ppm; or from 50 to 100 ppm; or from 25 to 50 ppm; or from 10 to 25
ppm; or from 5 to 10 ppm; or less than or equal to 5 ppm, and, for
example, from 1 to 5 ppm; or alternatively [0039] comprise at least
one compound from among F-1230xa, F-240fa and F-240db, in a content
of less than or equal to 0.5%; or less than or equal to 1000 ppm;
or less than or equal to 250 ppm; or from 150 to 200 ppm; or from
100 to 150 ppm; or from 50 to 100 ppm; or from 25 to 50 ppm; or
from 10 to 25 ppm; or from 5 to 10 ppm; or less than or equal to 5
ppm, and, for example, from 1 to 5 ppm.
[0040] Other particularly undesirable impurities mixed in the
reaction medium are also chlorinated molecules containing four
carbon atoms. These high-boiling compounds also accumulate in the
reactor, encumber the reaction volume and may lead, to a lesser
extent, by fluorination and rearrangement of the molecule to a
four-carbon fluorinated compound whose high toxicity is well known,
namely perfluoroisobutylene (PFIB).
[0041] These impurities contained in the starting material are
thus: [0042] molecules of the type such as chlorobutanes,
dichlorobutanes, trichlorobutanes and in particular the
tetrachlorobutane family such as 1,1,4,4-tetrachlorobutane,
1,2,3,4-tetrachlorobutane, 1,1,1,3-tetrachlorobutane and
1,1,3,3-tetrachlorobutane; [0043] molecules of the type such as
chlorobutenes, dichlorobutenes, tetrachlorobutenes and in
particular trichlorobutenes such as 1,2,4-trichlorobut-2-ene,
1,3-dichloro-2-chloromethylpropene, 1,1,3-trichlorobut-1-ene,
4,4,4-trichlorobut-1-ene, 1,2,3-trichloro-1-butene,
3,4,4-trichloro-1-butene, 2-chloromethyl-3,3-dichloropropene,
1,1,4-trichlorobut-2-ene, 3,3,4-trichlorobut-1-ene,
1,1,3-trichlorobut-2-ene, 1,3,3-trichlorobut-1-ene,
1,1,2-trichlorobut-1-ene, 1,1,1-trichlorobut-2-ene,
1,1,4-trichlorobut-2-ene, 1,3,4-trichlorobut-1-ene,
1,1,2-trichlorobut-2-ene, 1,2,3-trichlorobut-2-ene,
2-methyl-1,1,3-trichloro-1-propene, 1,2,4-trichlorobut-2-ene,
2,3,4-trichlorobut-1-ene.
[0044] Thus, advantageous compositions according to the invention:
[0045] comprise at least one compound from among the chlorobutane
series in a content of less than or equal to 0.5%; or less than or
equal to 1000 ppm; or less than or equal to 250 ppm; or from 150 to
200 ppm; or from 100 to 150 ppm; or from 50 to 100 ppm; or from 25
to 50 ppm; or from 10 to 25 ppm; or from 5 to 10 ppm; or less than
or equal to 5 ppm, and, for example, from 1 to 5 ppm; or
alternatively [0046] comprise a compound from among the
chlorobutene series, the total content of all these compounds being
less than or equal to 0.5%; or less than or equal to 1000 ppm; or
less than or equal to 250 ppm; or from 150 to 200 ppm; or from 100
to 150 ppm; or from 50 to 100 ppm; or from 25 to 50 ppm; or from 10
to 25 ppm; or from 5 to 10 ppm; or less than or equal to 5 ppm,
and, for example, from 1 to 5 ppm; or alternatively [0047] comprise
at least one compound from among the chlorobutanes and
chlorobutenes, in a content of less than or equal to 0.5%; or less
than or equal to 1000 ppm; or less than or equal to 250 ppm; or
from 150 to 200 ppm; or from 100 to 150 ppm; or from 50 to 100 ppm;
or from 25 to 50 ppm; or from 10 to 25 ppm; or from 5 to 10 ppm; or
less than or equal to 5 ppm, and, for example, from 1 to 5 ppm.
[0048] Other particularly undesirable impurities mixed in the
reaction medium are also molecules containing an oxygen heteroatom
such as acids, esters, aldehydes or oxychlorides, especially
phosgene. This compound is particularly known for its toxicity. In
the presence of hydrogen fluoride, these oxygenated compounds are
liable to decompose to form water. Water is an element whose
content must be minimized since it can accentuate corrosion
phenomena in HF medium.
[0049] Thus, advantageous compositions according to the invention:
[0050] comprise at least one oxygenated compound, in a content of
less than or equal to 0.5%; or less than or equal to 1000 ppm; or
less than or equal to 250 ppm; or from 150 to 200 ppm; or from 100
to 150 ppm; or from 50 to 100 ppm; or from 25 to 50 ppm; or from 10
to 25 ppm; or from 5 to 10 ppm; or less than or equal to 5 ppm,
and, for example, from 1 to 5 ppm.
Preparation of the Compositions According to the Invention
[0051] The compositions of the invention may be efficiently
obtained from carbon tetrachloride via F-240fa, by: [0052] reaction
of carbon tetrachloride with vinyl chloride to produce F-240fa;
[0053] dehydrochlorination of F-240fa to obtain F-1230za.
[0054] Alternatively, the process for preparing the compositions
comprises the following steps: [0055] reaction of carbon
tetrachloride with ethylene to produce F-250fb; [0056] chlorination
reaction of F-250fb (1,1,1,3-tetrachloropropane) to manufacture
predominantly F-240fa; [0057] dehydrochlorination of F-240fa to
obtain F-1230za.
[0058] The compositions according to the invention may then be
obtained by performing one or more steps for separating F-1230za
from the other compounds mentioned above, and especially from
F-240fa (which is generally the major side product of the
dehydrochlorination) and also other
telomerization/dehydrochlorination side products such as F-240db
and/or F-1230xa.
[0059] These separation steps may preferably be performed by
absorption/washing and distillation. As an alternative to
distillation or in combination therewith, it is also possible to
envisage separation by extractive distillation, physicochemical
separations on molecular sieves, alumina or active charcoal or
membrane separation.
[0060] A first separation is generally performed using standard
distillation (plate column, packing column) at atmospheric pressure
or under reduced pressure. The chosen pressure is less than 760
mmHg, preferentially less than 450 mmHg and more preferentially
less than 200 mmHg. Inherently, the column pressure determines the
temperature conditions for a chosen degree of separation. F-1230za
may be recovered by performing the distillation at a temperature
below 180.degree. C., preferentially below 160.degree. C. and more
preferentially below 130.degree. C. A single column or a
distillation train may be used. Under chosen conditions, the purity
of the F-1230za after distillation reaches a minimum of 99.3%.
[0061] A second separation may be performed using adsorption on
zeolite or active charcoal.
[0062] The zeolites or active charcoals that may be used in the
process for purifying F-1230za advantageously have a mean pore size
of from 3.4 to 11 .ANG., preferably from 3.4 to 10 .ANG. and even
more advantageously between 4 and 9 .ANG..
[0063] If the zeolite or active charcoal has a mean pore size of
greater than 11 .ANG., the amount of F-1230za adsorbed increases,
whereas if the mean pore size is less than 3.4 .ANG., the
adsorption capacity of the zeolite or active charcoal is
reduced.
[0064] The zeolite preferably has an Si/Al ratio of 2 or less. If
the Si/Al ratio of the zeolite is greater than 2, certain
impurities are liable to be not selectively adsorbed. The zeolite
is preferably at least one element chosen from the group consisting
of 4A molecular sieves, 5 .ANG. molecular sieves, 10.times.
molecular sieves and 13.times. molecular sieves.
[0065] The zeolite and the active charcoal are preferably used
individually for the purpose of regenerating the adsorbent, but
they may also be used as a mixture. The proportions of zeolite and
of active charcoal in the mixture are not particularly large.
[0066] To treat F-1230za with zeolite and/or active charcoal in the
liquid phase, use may be made of a batch process or a continuous
process. Industrially, a process consisting in continuously passing
F-1230za through a fixed bed is preferable. The liquid hourly space
velocity (LHSV) may be chosen appropriately as a function of the
content of impurities to be removed and of the amount of F-1230za
to be treated. In general, the space velocity is preferably from 1
to 50 h.sup.-1. Industrially, the purification process may
alternatively use two adsorption towers.
[0067] The treatment temperature for F-1230za is from 0.degree. C.
to 120.degree. C., preferably from 20.degree. C. to 80.degree. C.
If the treatment temperature is above 120.degree. C., the cost of
the equipment may increase on account of the heating of the
apparatus, whereas if the treatment temperature is below 0.degree.
C. cooling equipment may be necessary. The pressure is from 0 to 3
MPa and preferably from 0 to 1 MPa. If the pressure is greater than
3 MPa, the profitability may decrease on account of the
requirements in terms of pressure resistance of the apparatus.
[0068] A membrane separation technique may also be used in addition
to adsorption on active charcoal or on zeolite, or else as an
alternative to these techniques. Membrane separation may be
performed in the gas phase via a continuous process implemented at
low pressure, or at reduced pressure. The chosen pressure is less
than 5 bar, preferentially less than 2 bar and more preferentially
less than atmospheric pressure. The choice of the membrane depends
on the properties of the impurities to be separated from the
F-1230za (difference in solubility, diffusivity and permeability).
The membrane separation is performed at a temperature that depends
on the chosen pressure, below 250.degree. C., preferentially below
230.degree. C. and more preferentially below 180.degree. C.
[0069] According to a preferred embodiment, several separation
techniques are combined, such as distillation or extractive
distillation followed by separation by adsorption onto molecular
sieves. The zeolites that may be used in the process for purifying
F-1230za advantageously have a mean pore size of from 3.4 to 11
.ANG., preferably from 3.4 to 10 .ANG. and even more advantageously
between 4 and 9 .ANG.. The adsorption step is performed at a
temperature of between 0 and 120.degree. C., advantageously between
5 and 100.degree. C. and preferably between 10 and 80.degree.
C.
[0070] When F-1230za containing impurities is placed in contact
with zeolite and/or active charcoal in the liquid phase and/or is
purified on a membrane in the gas phase under the conditions
described above, F-1230za may be obtained in a purity of greater
than 99.9%.
[0071] Manufacture of F-1233zdE
[0072] The compositions according to the invention may be used for
the manufacture of F-1233zdE, F-1234zeE and/or F-245fa via one or
more fluorination steps, preferably in a single step.
[0073] The fluorination is a fluorination not catalyzed with HF in
the liquid phase. By adjusting the operating conditions
(temperature, pressure), the formation of F-1234ze and/or F-245fa
can be promoted to increase their content in the resulting stream.
Increasing the content of F-1234ze may also be obtained in another
embodiment by recycling the F-1233zd and F-245fa into the reactor
after separation of the F-1234ze. Increasing the content of F-245fa
may also be obtained in another embodiment by recycling the
F-1233zd and F-1234ze into the reactor after separation of the
F-245fa.
[0074] The liquid-phase fluorination reaction may be performed:
[0075] with an HF/1,1,3,3-tetrachloropropene mole ratio preferably
between 5 and 15, preferably between 6 and 15, even more
preferentially between 8 and 15, advantageously between 9 and 14
and preferentially between 9 and 12. The
HF/1,1,3,3-tetrachloropropene mole ratio includes the recycled
portion of HF and is preferably measured at the reactor inlet.
[0076] at a reaction temperature preferably between 80 and 120 and
advantageously between 90 and 110.degree. C. [0077] at a pressure
of between 5 and 20 bar, preferentially between 5 and 15 bar, even
more preferentially between 7 and 15 bar and advantageously between
7 and 12 bar.
[0078] The fluorination reaction is preferably performed in a
non-stirred reactor.
[0079] The reactor is preferably a metallic reactor. The metal of
the reactor may be steel or stainless steel. However, other
materials such as a super-austenitic stainless steel or an alloy
based on passivatable nickel may be used. The absence of catalyst
for the reaction is an advantage which makes it possible to prevent
corrosion phenomena known to those skilled in the art when a
fluorination catalyst is used in this type of reactor.
[0080] A removal pipe makes it possible to purge an amount of
undesirable products of high molecular weight that might have
formed during the fluorination reaction. This stream also contains
HF and upgradable organic compounds which are separated out via a
specific treatment before being returned into the reactor, using,
for example, decantation or azeotropic distillation, and preferably
a combination of the two.
[0081] The process according to the present invention for
fluorinating the composition thus separated out may be performed in
continuous, discontinuous or batch mode. In a preferred embodiment,
the process is performed in continuous mode.
[0082] The stream of products derived from the fluorination may
undergo suitable treatments (distillation, washing, etc.) so as to
recover the F-1233zdE in purified form and to separate it from the
other compounds present (HCl, unreacted HF, cis-1233zd isomer,
other organic compounds). One or more streams may be subjected to
recycling.
[0083] Thus, in a preferred embodiment, the invention relates to a
process for manufacturing, performed by fluorination, in the liquid
phase and in the absence of catalyst, F-1233zd, and/or F-1234ze
and/or F-245fa, comprising the steps: [0084] of introducing into a
fluorination reactor a stream comprising the composition of
1,1,3,3-tetrachloropropene (F-1230za), or a mixture of
1,1,3,3-tetrachloropropene and 1,3,3,3-tetrachloropropene
(F-1230zd), according to the invention.
[0085] The process is especially useful for preparing
trans-1-chloro-3,3,3-trifluoropropene (F-1233zdE) or
trans-1,3,3,3-tetrafluoropropene (F-1234zeE).
[0086] Finally, the invention relates more generally to the use of
the compositions according to the invention for manufacturing
F-1233zdE in a high purity of the order of 99.9%, and comprising a
reduced content of particular impurities.
[0087] A particular impurity consists of the isomer 1233xf
(2-chloro-3,3,3-trifluoropropene) which may be derived from the
chloro compounds 240db or 1230xa. The boiling point of this isomer
is relatively close to our final compound and might lead to
separation problems.
[0088] Other impurities whose boiling point is also close to that
of the compound F-1233zd and containing four carbons may originate
from the fluorination of chlorobutenes and/or chlorobutanes and may
prove to be an interference in the process since they are difficult
to separate out. These impurities are chosen from the following
list: [0089] 1,1,1-trifluorobutane or F-383mff or
CF.sub.3--CH.sub.2--CH.sub.2--CH.sub.3 [0090]
1,1,1,4,4-pentafluorobutane or F-365mff or
CF.sub.3--CH.sub.2--CH.sub.2--CHF.sub.2 [0091]
2,2,3,3-tetrafluorobutane or F-374scc or
CH.sub.3--CF.sub.2--CF.sub.2--CH.sub.3 [0092]
1,1,1,2,2,4,4,4-octofluorobutane or F-338mcf or
CF.sub.3--CF.sub.2--CH.sub.2--CF.sub.3 [0093]
1,1,1,2,2,3,3-heptafluorobutane or F-347mcc or
CF.sub.3--CF.sub.2--CF.sub.2--CH.sub.3 [0094]
1,1,1,2,2,3,3,4,4-nonafluorobutane or F-329mcc or
CF.sub.3--CF.sub.2--CF.sub.2--CH F.sub.2.
[0095] Other impurities whose boiling point is also close to that
of the compound F-1233zd and containing three carbons may originate
from the fluorination of chloropropenes and/or chloropropanes and
may prove to be an interference in the process since they are
difficult to separate out. These impurities are chosen from the
following list: [0096] 1,2-difluoropropane or F-272ea or
CH.sub.2F--CHF--CH.sub.3 [0097] 1,1,2-trifluoropropane or F-263eb
or CHF.sub.2--CHF--CH.sub.3 [0098] 1,2,2,3-tetrafluoropropane or
F-254ca or CH.sub.2F--CF.sub.2--CH.sub.2F.
EXAMPLES
[0099] The following examples illustrate the invention without
limiting it.
[0100] A first step consists in preparing the starting material.
1,1,3,3-Tetrachloropropene is obtained by dehydrochlorination of
1,1,1,3,3-pentachloropropane in the presence of anhydrous ferric
chloride.
Example 1: Preparation of F-1230za by Dehydrochlorination of
F-240fa
[0101] 1626.5 g of 99.6% pure 1,1,1,3,3-pentachloropropane are
placed in a jacketed glass reactor equipped with a reflux
condenser. The reactor headspace is flushed with a stream of 4 l/h
of nitrogen to render the atmosphere inert. 17 g of anhydrous
ferric chloride are then introduced, followed by starting the
stirring at 800 rpm. The reflux is fed by a fluid maintained at
20.degree. C. The gas outlet of the condenser is connected to a
water bubbler which allows the HCl that is evolved in the course of
the dehydrochlorination reaction to be trapped. The mixture is then
heated at 80.degree. C. for 5 hours. 1338.1 g of resulting solution
are emptied from the round-bottomed flask. The mixture obtained is
filtered to remove the ferric chloride in suspension, purified with
active charcoal and then analyzed by gas chromatography.
TABLE-US-00001 TABLE 1 dehydrochlorination of 240fa: composition of
the mixture Compound (weight %) Before reaction After reaction
1230za 0.046 92.25 250fb 0.029 0.024 240fa 99.61 3.10
C.sub.2Cl.sub.6 0.059 0.066 240db 0.157 0.187 Chlorobutenes +
chlorobutanes 0.083 0.127 Chloropropenes + chloropropanes 0.003
0.134
[0102] The chlorobutenes and chlorobutanes were able to be
identified only by their empirical formula as
C.sub.4H.sub.6Cl.sub.2, C.sub.4H.sub.7Cl.sub.3,
C.sub.4H.sub.2Cl.sub.4 or C.sub.4H.sub.6Cl.sub.4. The
chloropropenes and chloropropanes are 1230xa and other compounds
identified by their empirical formula as C.sub.3H.sub.3Cl.sub.3, or
C.sub.3H.sub.2Cl.sub.4 which are different from 250fb, 240fa or
240db.
[0103] The remainder of the above compositions is constituted of
unidentified products.
Example 2: Distillation of 1230za
[0104] 1230za of low purity is then subjected to standard
laboratory distillation involving a 10-plate Oldershaw column, a
condenser, a vacuum pump, a round-bottomed flask and receiver
flasks. The distillation is performed under a vacuum of 25 mbar,
and the product 1230za then has a boiling point of 53.degree. C.
The result of the distillation is illustrated in table 2.
TABLE-US-00002 TABLE 2 distillation of 1230za: composition of the
mixture Compound (weight %) Before distillation After distillation
1230za 92.25 99.30 250fb 0.024 0.021 240fa 3.10 0.179
C.sub.2Cl.sub.6 0.066 0.012 240db 0.187 0.001 Chlorobutenes +
chlorobutanes 0.127 0.133 Chloropropenes + chloropropanes 0.134
0.245
Example 3: Batch-Mode Fluorination of 1230za
[0105] The tests performed are batch tests at a regulated pressure.
100 g of 99.6% pure F-1230za and 115 g of HF, i.e. a mole ratio of
10.3, are successively introduced into the 1-liter stainless-steel
autoclave, equipped with a condenser, a pressure indicator, a
thermometer probe and a rupture disk. A cooling circulation is
established in the condenser, the reactor is heated to about and
the pressure gradually increases to reach 10 bar (nominal
pressure); the temperature measured is then 85.degree. C. in the
reactor. At this pressure, opening of the regulating valve makes it
possible to remove the light compounds. The organic products are
washed and then trapped. After 24 hours, the system is returned to
room temperature. The rest of the organic compounds and of the
hydracids are removed from the reactor by degassing followed by
flushing with helium. This results in 138 g of hydracids, 61 g of
trapped organic compounds and 1.5 g of heavy black compounds at the
bottom of the reactor. The weight percentage distribution of the
organic compounds is as follows: 94.9% of E-1233zd, 3.3% of
Z-1233zd, 0.8% of 245fa, 0.3% of E-1234ze, and also intermediate
compounds such as 1232zd (1,3-dichloro-3,3-difluoroprop-1-ene) or
1232za (1,1-dichloro-3,3-difluoroprop-1-ene).
[0106] No trace of 1230za was found, thus illustrating total
conversion of the reagent. The conversion is very high and the
final yield of desired product E-1233zd close to 95%.
Comparative Example 4: Liquid-Phase Batch Fluorination of 240fa
[0107] A test is performed according to Example 3 by introducing
550 g of F-240fa and 580 g of HF, i.e. a mole ratio of 11. This
results in 570 g of hydracids, 545 g of organic compounds and 6.1 g
of heavy compounds. The weight percentage distribution of the
organic compounds is as follows: 75.7% of F-240fa, 12.6% of
F-241fa, 7.1% of E-1233zd, 0.2% of Z-1233zd, 3.9% of 245fa and
0.07% of intermediate compounds (1232, 242).
[0108] The degree of conversion of the F-240fa in non-catalyzed
liquid phase is thus very low and the yield of desired product
E-1233zd very low.
Comparative Example 5: Liquid-Phase Batch Fluorination of a
240db/240aa Mixture
[0109] The procedure of Example 3 is reproduced. The organic
compound is a 240db/240aa mixture (88.5%/11.5%). 108 g of organic
mixture and 101 g of HF are successively introduced into the
autoclave, i.e. a mole ratio of 10.3. This results in 96 g of
hydracids, 90 g of organic compounds and 2.2 g of heavy compounds.
The weight percentage distribution of the organic compounds is as
follows: 86.2% of F-240db, 11.9% of F-240aa, 1.3% of an isomer
241.
[0110] The degree of conversion of the F-240db and of the F-240aa
in non-catalyzed liquid phase is thus very low and the yield of
desired product E-1233zd nonexistent.
Comparative Example 6: Liquid-Phase Batch Fluorination of
1230xa
[0111] The procedure of Example 3 is reproduced. The organic
compound is 1230xa. 90 g of 1230xa and 80 g of HF are successively
introduced into the autoclave, i.e. a mole ratio of 8. This results
in 90.5 g of hydracids and 66.3 g of organic compounds. The weight
percentage distribution of the organic compounds is as follows:
1.2% of 1230xa, 8.7% of an isomer 1232 and 90% of unidentified
heavy compounds.
[0112] The degree of conversion of the 1230xa in non-catalyzed
liquid phase is high, but does not lead to the desired product,
E-1233zd. It rapidly converts into heavy compounds that are
difficult to identify.
[0113] Examples 3 to 6 show the results obtained for the
non-catalyzed fluorination reaction for the following reagents:
1230za, 240fa, 240db, 240aa and 1230xa. With the exception of
1230za, all the other yields of E-1233zd are very low.
Embodiments
[0114] 1. A composition comprising at least 99.5% by weight of
1,1,3,3-tetrachloropropene (F-1230za), or a mixture of
1,1,3,3-tetrachloropropene and of 1,3,3,3-tetrachloropropene
(F-1230zd), and at least one additional compound chosen from a list
of compounds consisting of pentachloropropanes, tetrachloropropenes
other than F-1230za and F-1230zd, chlorobutenes, chlorobutanes and
oxygenated compounds, said compound and/or the total amount of said
compounds being present in the composition in a content of less
than or equal to 0.5% by weight. [0115] 2. The composition as in
embodiment 1, in which said additional compound represents a
content of less than or equal to 1000 ppm; or less than or equal to
500 ppm; or less than or equal to 450 ppm; or less than or equal to
400 ppm; or less than or equal to 350 ppm; or less than or equal to
300 ppm; or less than or equal to 250 ppm; or less than or equal to
200 ppm; or less than or equal to 150 ppm; or less than or equal to
100 ppm; or less than or equal to 75 ppm; or less than or equal to
50 ppm; or less than or equal to 25 ppm; or less than or equal to
10 ppm; or less than or equal to 5 ppm, in the composition. [0116]
3. The composition as in embodiment 2, in which said additional
compound is or are chosen from 1,1,1,3,3-pentachloropropane
(F-240fa), 1,1,1,2,3-pentachloropropane (F-240db) and
1,1,2,3-tetrachloropropene (F-1230xa). [0117] 4. A process for
manufacturing the composition as in any one of embodiments 1 to 3,
comprising the following steps: [0118] reaction of carbon
tetrachloride with vinyl chloride to produce
1,1,1,3,3-pentachloropropane (F-240fa); [0119] dehydrochlorination
of F-240fa to obtain 1,1,3,3-tetrachloropropene (F-1230za); [0120]
one or more steps for separating out the F-1230za. [0121] 5. A
process for manufacturing the composition as in any one of
embodiments 1 to 3, comprising the following steps: [0122] reaction
of carbon tetrachloride with ethylene to produce
1,1,1,3-tetrachloropropane (F-250fb); [0123] chlorination of
F-250fb to obtain 1,1,1,3,3-pentachloropropane (F-240fa); [0124]
dehydrochlorination of F-240fa to obtain 1,1,3,3-tetrachloropropene
(F-1230za); [0125] one or more steps for separating out the
F-1230za. [0126] 6. The process as in embodiments 4 or 5, in which
the separation is performed by distillation or extraction, and/or
by physicochemical separation on molecular sieves, alumina or
active charcoal, and/or by membrane separation, optionally in the
gas phase. [0127] 7. The process as in embodiment 6, in which a
first separation step is performed via one or more distillations
and a second separation step is performed by adsorption on
molecular sieves, on active charcoal or on a mixture thereof.
[0128] 8. The process as in embodiment 6 or 7, in which the
separation step is performed by adsorption on zeolite, of the type
such as 4A, 5A, 10.times. or 13.times. molecular sieves, and
optionally followed by gas-phase membrane separation. [0129] 9. The
process as in any one of embodiments 6, 7 and 8, in which the step
of separation by adsorption is performed at a temperature of
between 0 and 120.degree. C. and preferably between 20 and
80.degree. C. [0130] 10. The use of the composition as claimed in
any one of embodiments 1 to 5 in the manufacture of
1-chloro-3,3,3-trifluoropropene (F-1233zd),
1,3,3,3-tetrafluoropropene (F-1234ze) or
1,1,1,3,3-pentafluoropropane (F-245fa). [0131] 11. A process for
manufacturing 1-chloro-3,3,3-trifluoropropene (F-1233zd), and/or
1,3,3,3-tetrafluoropropene (F-1234ze) and/or
1,1,1,3,3-pentafluoropropane (F-245fa), by fluorination performed
in the liquid phase and in the absence of catalyst, comprising the
steps: [0132] of introducing into a fluorination reactor a stream
comprising the composition as in any one of embodiments 1 to 3.
[0133] 12. The process as in embodiment 11 for forming
trans-1-chloro-3,3,3-trifluoropropene (F-1233zdE) or
trans-1,3,3,3-tetrafluoropropene (F-1234zeE). [0134] 13. The
process as in embodiments 11 or 12, followed by one or more steps
for separating 1-chloro-3,3,3-trifluoropropene (F-1233zd), and/or
1,3,3,3-tetrafluoropropene (F-1234ze) and/or
1,1,1,3,3-pentafluoropropane (F-245fa) from the stream of
products.
* * * * *