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.

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 or 13 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 C. and preferably between 20 and 80 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

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 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 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 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 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 or 13 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 C. and preferably between 20 and 80 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.