COMPOSITIONS CONTAINING 1,1,1,3,3-PENTACHLOROPROPANE

Abstract

The invention first relates to a composition comprising at least 99 wt. % of 1,1,1,3,3-pentachloropropane and at least one compound selected from a list of additional compounds consisting of dichloropropanes, trichloropropanes, tetrachloropropanes, pentachloropropanes different from 1,1,1,3,3-pentachloropropane, hexachloropropanes, heptachloropropanes, chloropropenes, dichloropropenes, trichloropropenes, tetrachloropropenes, pentachloropropenes and hexachloropropene, the weight content of said compound in the composition being lower than or equal to 500 ppm.

Claims

1-14. (canceled)

15. A composition comprising at least 99% by weight of 1,1,1,3,3-pentachloropropane and at least one additional compound selected from the group consisting of dichloropropanes, trichloropropanes, tetrachloropropanes, pentachloropropanes other than 1,1,1,3,3-pentachloropropane, hexachloropropanes, heptachloropropanes, chloropropenes, dichloropropenes, trichloropropenes, tetrachloropropenes, pentachloropropenes and hexachloropropene, said at least one additional compound being present in the composition in a weight content of less than or equal to 500 ppm.

16. The composition as claimed in claim 15, in which said at least one additional compound is present in the composition in a weight content of less than or equal to 250 ppm.

17. The composition as claimed in claim 15, comprising a plurality of additional compounds selected from the group consisting of dichloropropanes, trichloropropanes, tetrachloropropanes, pentachloropropanes other than 1,1,1,3,3-pentachloropropane, hexachloropropanes, heptachloropropanes, chloropropenes, dichloropropenes, trichloropropenes, tetrachloropropenes, pentachloropropenes and hexachloropropene, each of the additional compounds of said plurality of additional compounds being present in the composition in a weight content of less than or equal to 500 ppm.

18. The composition as claimed in claim 15, comprising a plurality of additional compounds selected from the group consisting of dichloropropanes, trichloropropanes, tetrachloropropanes, pentachloropropanes other than 1,1,1,3,3-pentachloropropane, hexachloropropanes, heptachloropropanes, chloropropenes, dichloropropenes, trichloropropenes, tetrachloropropenes, pentachloropropenes and hexachloropropene, the total weight content of all of the additional compounds being less than or equal to 1000 ppm.

19. The composition as claimed in claim 15, comprising at least 99.5% by weight of 1,1,1,3,3-pentachloropropane.

20. The composition as claimed in claim 15, comprising at least one additional compound selected from the group consisting of hexachloropropene and heptachloropropanes, wherein the weight content of each of these additional compounds in the composition is less than or equal to 500 ppm.

21. The composition as claimed in claim 15, comprising at least one additional compound selected from the group consisting of pentachloropropenes and hexachloropropanes, wherein the weight content of each of these additional compounds in the composition is less than or equal to 500 ppm.

22. The composition as claimed in claim 15, comprising at least one additional compound selected from the group consisting of tetrachloropropenes and pentachloropropanes other than 1,1,1,3,3-pentachloropropane, wherein the weight content of each of these additional compounds in the composition is less than or equal to 500 ppm.

23. The composition as claimed in claim 15, comprising at least one additional compound selected from the group consisting of 2,3,3,3-tetrachloropropene, 1,1,2,3-tetrachloropropene, 1,1,1,2,3-pentachloropropane, 1,1,2,2,3-pentachloropropane and 1,1,1,2,2-pentachloropropane, wherein the weight content of each of these additional compounds in the composition is less than or equal to 500 ppm.

24. The composition as claimed in claim 15, comprising at least one additional compound selected from the group consisting of trichloropropenes and tetrachloropropanes, wherein the weight content of each of these additional compounds in the composition is less than or equal to 500 ppm.

25. The composition as claimed in claim 15, comprising at least one additional compound selected from the group consisting of 1,1,3-trichloropropene, 3,3,3-trichloropropene, 1,1,1,3-tetrachloropropane, 1,1,2,3-tetrachloropropane and 1,1,1,2-terachloropropane, wherein the weight content of each of these compounds in the composition is less than or equal to 500 ppm.

26. A process for producing 1,3,3,3-tetrafluoropropene, especially in trans form, comprising: providing the composition as claimed in claim 15; and reacting the composition with hydrofluoric acid.

27. The process as claimed in claim 26, comprising a single step of catalytic fluorination.

28. The process as claimed in claim 26, comprising two successive steps of catalytic fluorination, the steps comprising: reacting the composition of claim 15 with hydrofluoric acid in the gas phase, to manufacture an intermediate product; optionally, purifying the intermediate product; and then reacting the intermediate product with hydrofluoric acid in the gas phase, to manufacture 1,3,3,3-tetrafluoropropene.

29. The process as claimed in claim 26, wherein the intermediate product comprises 1-chloro-3,3,3-trifluoropropene in trans form.

Description

EXAMPLES

[0254] The following examples illustrate the invention without limiting it.

Example 1

Analysis of Two Compositions Based on F-240fa

[0255] Two compositions A and B based on F-240fa, of different purities, are considered. The first composition A results from a synthesis and from a purification in the laboratories of the applicant company. The second composition B originates from a commercial supplier, Synquest Laboratories.

[0256] The compositions in mol % of these two samples are given in table 1 below (after gas chromatography analysis).

TABLE-US-00002 TABLE 1 Analysis of compositions A and B Composition A Composition B F-1230za 0.055 0.018 F-250 0.035 0.449 F-240fa 99.58 96.79 C.sub.2Cl.sub.6 0.051 0.239 F-240db 0.157 2.46 Others 0.122 0.044

Example 2

Preparation of the Fluorination Catalyst

[0257] 343 g of a Grace HSA alumina support, pretreated in the fixed bed at 280° C. under a HF/air mixture containing between 5 and 10% of HF, are placed in a rotary evaporator. The starting alumina is provided in the form of beads with a diameter of between 0.5 and 2 mm. Its specific surface is approximately 220 m.sup.2/g and its pore volume is 1.3 cm.sup.3/g. Furthermore, two aqueous solutions are prepared: [0258] one contains 81 g of methanol and 8 g of water; [0259] the other contains 62 g of water, 55 g of chromic acid CrO.sub.3 and 130 g of nickel chloride NiCl.sub.2 (dissolution of the mixture at 50° C. for 2h30).

[0260] The two solutions are introduced simultaneously and gradually onto the alumina support maintained at 40° C. and stirred. After a step of maturing under nitrogen, the catalyst is dried under nitrogen, then under vacuum at 65° C., and then at approximately 90° C. for six hours.

[0261] 500 g of impregnated solid are charged to a tubular Inconel reactor. The catalyst is first of all dried while flushing with nitrogen at 320° C., at atmospheric pressure. It is subsequently fluorinated in the presence of a HF/N.sub.2 (5 to 10% of HF in nitrogen) mixture at 320° C. and then up to 390° C. The HF feed is subsequently cut off. The catalyst is cooled under nitrogen.

Example 3

Gas-Phase Fluorination

[0262] The example was carried out using a continuous gas-phase fluorination pilot plant. This pilot plant comprises a reactor consisting of an Inconel tube with an internal diameter of 38 mm and with a length of 500 mm, placed vertically in a tubular electric furnace. A thermometer well with an external diameter of 6 mm is placed coaxially in the furnace and makes possible a reading of temperature along the catalytic bed using four stage thermocouples.

[0263] A coil wound around the reactor and traversed vertically from the bottom upward makes it possible to preheat the reactants before entry into the reactor. A 30 mL layer of corundum above the catalytic bed makes it possible to provide a homogeneous distribution of the gaseous reactants. A regulating valve makes it possible to maintain the desired pressure. The gas stream at the inlet and the outlet of the reactor is analyzed by gas chromatography.

[0264] An appropriate amount of solids described above is introduced into the reactor and then dried overnight in the presence of nitrogen at 250° C. and atmospheric pressure. The dried solid is subsequently activated (still at atmospheric pressure) under a stream comprising nitrogen and anhydrous hydrofluoric acid for 15 minutes before being placed under pure HF at 250° C. The pressure is subsequently very gradually regulated until 10 bar absolute are reached. The reactants (the chlorine and the composition A) are subsequently introduced. The flow rates fed are such that the HF/F-240fa mole ratio is equal to 20, the Cl.sub.2/F-240fa mole ratio is equal to 0.018 and the contact time is 15 seconds. The temperature is maintained at 250° C. The composition of the gas stream exiting from the reactor is analyzed by gas chromatography and is given in table 1.

[0265] The experiment is also repeated under the same operating conditions with the sample B of F-240fa containing 2.46% of F-240db. The composition of the gas stream exiting from the reactor is analyzed by gas chromatography and is given in table 2 below in mol %.

TABLE-US-00003 TABLE 2 Gas-phase fluorination of compositions based on F-240fa the production of F-1233zdE Reaction with the Reaction with the composition A composition B F-1233zdE 80.2 78.6 F-1233zdZ 12.8 11.7 F-243fa 0.7 0.5 F-244fa 2.6 3.1 F-245fa 1.4 2 F-1233xf 0.14 2.12 F-1234zeE 1.9 1.81 F-1234zeZ 0.1 0.09 F-1232zd 0.09 0.03 F-1232za 0.07 0.05

Example 4

Demonstration of the Polymerization of F-1233xf

[0266] A 100 mL autoclave equipped with a temperature measurement and with a pressure measurement is available. This autoclave is immersed in an oil bath, the temperature of which is regulated. 49.2 g of compound F-1233xf with a purity of 99.67% are introduced into the autoclave and the temperature of the reactor is increased to 56° C. The autogenous relative pressure is then 2.8 bar. The compound is left at temperature for 18 hours. On conclusion of this period, the reactor is brought back to ambient temperature and then depressurized toward a stainless steel trap cooled in liquid nitrogen. The cold trap is subsequently reduced in pressure and then analyzed: 99.67% of F-1233xf are obtained. The composition of the product recovered after degassing is identical to the composition of the starting material. The visual appearance of the reactor bottom, where an oily film has been deposited, is noted. The autoclave is subsequently rinsed using a dichloromethane solution, which is analyzed by liquid chromatography. The analysis reveals the presence of 1100 ppm of a compound identified by the mass spectrometry-chromatography technique: C.sub.9F.sub.9H.sub.6Cl.sub.3, that is to say the trimer of the compound F-1233xf.

Example 5

Demonstration of the Polymerization of F-1233xf in an Acid Medium

[0267] Example 4 is repeated with 12.1 g of F-1233xf brought into the presence of 41.6 g of HF. The mixture is left under a temperature 79° C. and a relative autogenous pressure of 7.6 bar for 18 hours. The compound collected in the cold trap after depressurization, washing in a bubbler and drying still exhibits a purity of 99.67%. Under these operating conditions, the bottom of the reactor is covered with white crystals. Approximately 1 g of these crystals could be recovered. Analyses by infrared and by NMR made it possible to identify an oligopolymeric compound consisting of (—CClCF.sub.3—CH.sub.2—).sub.n groups.