ES2646006T3 - Process for the manufacture of 2-chloro-3,3,3-trifluoropropene (HCFO 1233xf) by liquid phase fluoridation of pentachloropropane - Google Patents

Abstract

Process of catalytic fluorination in liquid phase in an organic medium of 1,1,1,2,3-pentachloropropane product or of a mixture of 1,1,1,2,3-pentachloropropane and 1,1,2,2,3 -pentachloropropane, in 2-chloro-3,3,3-trifluoropropene in the presence of a catalyst that is an ionic liquid, said process being carried out in a solvent.

Description

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DESCRIPTION

Process for the manufacture of 2-chloro-3,3,3-trifluoropropene (HCFO 1233xf) by liquid phase fluorination of pentachloropropane

Field of the Invention

The object of the invention is the catalytic fluorination in the liquid phase of the product 1,1,1,2,3-pentacIoropropane (HCC 240db) or a mixture of HCC240db and 1,1,2,2,3-pentachloropropane (HCC 240aa) in the product 2-chloro-3,3,3-trifluoropropene (HCFO 1233xf).

Technical background

The Montreal protocol for the protection of the ozone layer led to the end of the use of chlorofluorocarbons (CFCs). Less aggressive compounds for the ozone layer, such as hydrofluorocarbons (HFCs), for example HFC-134a, have replaced chlorofluorocarbons. In fact, it was shown that these latter compounds produce greenhouse gases. There is a need for the development of technologies, which have a low ODP (ozone depletion potential) and a low GWP (global warming potential). Although hydrofluorocarbons (HFCs), which are compounds that do not affect the ozone layer, were identified as interesting candidates, they have a relatively high GWP value. There is still a need to find compounds that have a low GWP value. Hydrofluoroolefins (HFO) were identified as possible alternatives, with very low ODP and GWP values.

Several procedures were developed for the production of HFO compounds, in particular propenes. The two compounds 1233xf (2-chloro-3,3,3-trifluoropropene) and 1234yf (2,3,3,3-tetrafluoropropene) are particularly desirable.

WO2008 / 149011 describes the liquid phase fluorination in the presence of an ionic liquid of a propene. It is generally indicated that 1233xf and / or 1234yf (2,3,3,3-tetrafluoropropene) can be obtained by conversion of 1230xa.

WO2009 / 003157 describes in its example 3 a supposed procedure for the conversion of 240db. In this example, the reactor is first charged with Hf and the organic compound and then the reaction is said to proceed to product 245eb (1,1,1,2,3-pentafluoropropane).

WO2007 / 079431 in Example 3 describes the reaction of product 240aa in a NaOH solution to provide the corresponding unsaturated compound, which needs a subsequent and differentiated fluorination step for conversion into 1233xf.

WO90 / 08754 describes in example 4-1 the fluorination of 240aa. In this example, the reactor is charged with an organic compound and with HF, and the catalyst is antimony pentachloride. The reaction products comprise products of the series 241 (tetrachlorofluoropropane), 242 (trichlorodifluoropropane, 243 (dichlorotrifluoropropane) and 244 (chlorotetrafluoropropane).

EP 2 103 587 describes a process for the preparation of 2-chloro-3,3,3-trifluoropropene in the presence of a fluorinated C2O3 catalyst.

Thus, there is still a need for processes for the production of compound 1233xf.

Compendium of the invention

The invention provides a liquid phase catalytic fluorination process in an organic medium of the 1,1,1,2,3-pentachloropropane product or a mixture of 1,1,1,2,3-pentachloropropane and 1,1,2 , 2,3-pentachloropropane, in 2- chloro-3,3,3-trifluoropropene in the presence of a catalyst that is an ionic liquid, said process being carried out in a solvent.

Forms of realization are the following:

- the process is carried out in an organic medium, in a solvent, preferably present in an amount for a dilution ratio of at least 20%, preferably between 20% and 80%, advantageously between 40% and 60%. The solvent can be selected from 1,2-dichloroethane, 1,2,3-trichloropropane, 1-chloro-1-fluoroethane, 1,1-difluoroethane, 1,1-dichloroethane and 1,3-dichloro-1-fluorobutane, isomers of tetrachlorofluoropropane, trichlorodifluoropropane isomers and dichlorotrifluoropropane isomers, 1,1,1,3,3-pentafluorobutane and 1,1,2-trichloro-2,2-difluoroethane, nitrated solvents including nitromethane and nitrobenzene, sulfones including tetramethylenesulfone dimethylsulfone, 1,1,2-trichloro-2-fluoroethane or perchlorethylene, or mixtures thereof, preferably 1,1,2-trichloro-2,2-difluoroethane.

- the catalyst is an ionic liquid. The molar ratio of catalyst / organic compounds may be between 2 mol% and 90 mol%, preferably between 4 mol% and 80 mol% and more preferably between

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6 mol% and 75 mol%.

- Chlorine is added during the reaction, preferably according to a molar ratio of 0.05 to 20 mol%, preferably 0.5 to 15 mol% of chlorine per mole of starting compound.

- a gas, preferably anhydrous HCl, is injected. The gas flow, compared to the starting product flow is between 0.5: 1 and 5: 1, advantageously, between 1: 1 and 3: 1.

- the reaction product is extracted in a gaseous state.

- 1,1,1,2,2-pentachloropropane contains up to 20 mol% of 1,1,2,2,3-pentachloropropane isomer.

- the reaction temperature varies between 30 ° C and 200 ° C, preferably between 40 ° C and 170 ° C, advantageously between 50 ° C and 150 ° C.

- the reaction pressure is greater than 1x105 Pa (2 bar), preferably between 4x105 and 50 x105 Pa (4 and 50 bar), in particular between 5x105 and 25x105 (5 and 25 bar).

- the molar ratio of HF: starting compound is between 0.5: 1 and 50: 1, preferably between 3: 1 and 20: 1, advantageously approximately 5: 1.

- a stabilizer is used, preferably chosen from the group consisting of p-methoxyphenol, t-amylphenol, thymol, limonene, d, l-limonene, quinones, hydroquinones, epoxides, amines and mixtures thereof. The amount may be 5-1000 ppm, preferably 10-500 ppm.

- the method preferably comprises:

(i) contacting 1,1,1,2,3-pentachloropropane or a mixture of 1,1,1,2,3-pentachloropropane and 1,1,2,2,3-pentachloropropane with hydrogen fluoride in a liquid phase in an organic medium under conditions sufficient to form a reaction mixture comprising 2-chloro-3,3,3-trifluoropropene;

(ii) separating the reaction mixture into a first stream comprising HCl, and a second stream comprising HF and 2-chloro-3,3,3-trifluoropropene.

- the second stream comprises between 30 mol% and 70 mol% of 1233xf, between 30 mol% and 70 mol% of HF and less than 10 mol%, preferably less than 5 mol%, of compounds of the 242 and 243 series.

- step (ii) can be a distillation stage. The second stream can be further separated, preferably by decantation, in a stream of HF containing mainly HF, and an organic stream containing 2-chloro-3,3,3-trifluoropropene. The organic current can be further purified. The method may further comprise a purge stage to remove heavy materials formed during step (i).

- the procedure is carried out continuously.

Brief description of the drawings

- Figure 1 is a representation of the experimental device used in the examples;

- Figure 2 is a schematic representation of a procedure carried out by the invention.

Detailed description of embodiments

The invention is based on the surprising findings that 240db / 240aa can be fluorinated in liquid phase to give 1233xf, and that the process conditions can be selected so that the reaction is achieved with a substantial selectivity in the desired product.

The liquid phase procedure is carried out in an organic phase. The use of an organic phase instead of an HF phase favors the reaction at 1233xf. The prior art listed above describes reaction mixtures comprising a substantial part of HF, hence an acid phase. In an acid phase, only saturated products are produced. The applicant has discovered that, surprisingly, there are conditions that allow fluorination in 1233xf. Notably, when the reaction is carried out in an organic phase (comprising the starting material 240 and / or solvent), then 1233xf can be formed. When HF is added to an initial medium, it will not remain in the medium since it reacts and the amount of HF (or concentration) will be very low, compared to that of other products.

The term "organic phase" can be defined as referring to a reaction phase comprising the catalyst and the starting material and a solvent but substantially free of HF. Especially the

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Procedure carried out in an "organic phase" refers to the procedure in which the initial charge does not comprise any HF, in contrast to the prior art.

Due to the particular operating conditions, 1233xf gas can be extracted from the reactor under the gas phase, keeping the polymerization reactions at a low level.

Liquid phase fluoridation of 240db / 240aa at 1233xf is carried out in the presence of a catalyst.

The reaction is carried out in a liquid solvent medium, the reaction zone being either initially charged with a starting amount of organic material (the starting material) and / or the necessary amount of solvent, or fed in a manner Continue with this amount of solvent (possibly mixed previously with the raw material). It is preferred that the solvent be charged at the beginning; however, if necessary injections can be carried out in order to adjust the amount of solvent.

The reaction conditions (in particular the pressure) are such that the reactants are liquid. According to one embodiment, the reactants are liquid while the reaction product is gaseous. The fact that the reaction products are gaseous allows their recovery in a gaseous phase at the exit of the reaction zone. The intermediate product, especially compound 242 (trichlorodifluoropropane), is preferably liquid under the reaction conditions, although this can be separated in the gas flow.

According to the invention, this step is carried out in particular under a pressure greater than 2x105 Pa (2 bar). Advantageously, the pressure is between 4x105 Pa and 50x105 Pa (4 and 50 bar), in particular between 5x1o5 Pa and 25x105 Pa (5 and 25 bar).

For example, the reaction can be carried out at a temperature ranging between 30 ° C and 200 ° C, preferably between 40 ° C and 170 ° C, advantageously between 50 ° C and 150 ° C.

The molar ratio of HF: starting compound is generally between 0.5: 1 and 50: 1, preferably between 3: 1 and 20: 1. Values of 5: 1 can be used advantageously. The amount of HF added corresponds to the stoichiometry of the reaction (here 3), to which the amount of HF that is present in the output streams (HF and organic compounds) that are normally azeotropic mixtures will be added.

The rest of the reaction conditions, in particular the flow rates, can be determined by one skilled in the art according to the usual general knowledge, depending on the temperature, pressure, catalyst, reactant ratios and the like. Care must be taken that subsequent fluoridation reactions are avoided so that 1233xf is the main product obtained (apart from intermediate products).

The solvent is an inert organic solvent under the reaction conditions. Such a solvent will usually be saturated, advantageously in C2 to C6, in order to avoid the addition reactions. Such solvents may be, for example, those cited in patent application FR2733227. Such solvents have a boiling temperature (measured at atmospheric pressure), for example, greater than 40 ° C, advantageously greater than 50 ° C, in particular greater than 60 ° C. Higher reaction temperatures will involve higher pressures, so that the boiling temperature of the solvent under reaction conditions is higher than the temperature at which the reaction is carried out.

Particular mention may be made of the saturated compounds of ethane, propane or butane, substituted by at least two halogen atoms, chosen from chlorine and fluorine, or a mixture thereof. As an example, 1,2-dichloroethane, 1,2,3-trichloropropane, 1-chloro-1-fluoroethane, 1,1-difluoroethane, 1,1-dichloroethane and 1,3-dichloro-1-fluorobutane, isomers of tetrachlorofluoropropane, isomers of trichlorodifluoropropane and isomers of dichlorotrifluoropropane, 1,1,1,3,3-pentafluorobutane and 1,1,2-trichloro-2,2-difluoroethane, or a mixture thereof. Nitrated solvents such as nitromethane or nitrobenzene and sulfones such as tetramethylene sulfone (also known as sulfolane) or dimethylsulfone can also be used. A preferred solvent is 1,1,2-trichloro-2,2-difluoroethane (F122). Possibly reactive solvents may also be used, provided that the product of their reaction is a non-reactive solvent. For example, the precursor of F122 can be used, namely F121 (CC ^ F-CHCl, 1,1,2-trichloro-2-fluoroethane) or perchlorethylene.

The solvent may be present in an amount for a dilution ratio of at least 20%, preferably between 20% and 80%, advantageously between 40% and 60%.

The reaction is catalyzed. The catalyst used is an ionic liquid. These ionic liquids are particularly interesting for fluorination by liquid phase HF. The ionic liquids described in patent applications WO2008 / 149011 (in particular from page 4, line 1 to page 6, line 15, included, by reference) and WO01 / 81353 may be cited in the name of the applicant, as well as the reference "liquid-phase HF Fluorination", Multiphase Homogeneous Catalysis (Liquid Phase HF Fluoridation, Homogenea Mulfifasica Catalysis), Ed. Wiley-VCH, (2002), 535.

It can be operated with variable catalyst / organic compound ratios (including solvent if used), but in general it will be preferred that this molar ratio be between 2 mol% and 90 mol%, preferably between

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4 mol% and 80 mol% and more preferably between 6 mol% and 75 mol%.

The starting material may be substantially pure 240db, or a mixture of 240db and 240aa. In one embodiment, the starting material can be a typical 240db feed, that is, one containing the isomer 240aa in an amount of up to 20%.

A chlorine stream can be used to increase the shelf life of the catalyst, typically in an amount of 0.05 to 20 mol%, preferably 0.5 to 15 mol% of chlorine per mole of starting compound 240db / 240aa. Chlorine can be introduced pure or mixed with an inert gas such as nitrogen. The use of an ionic catalyst allows small amounts of chlorine to be used.

A raw material stabilizer can be used if necessary; typically in an amount of 5-1000 ppm, preferably 10-500 ppm. This stabilizer can be, for example, p-methoxyphenol, t-amylphenol, thymol, limonene, d, l-limonene, quinones, hydroquinones, epoxides, amines and mixtures thereof.

It is also possible that the reaction product is separated using a light gas that allows its advance by mechanical drag. Removing l233xf gaseous from the liquid phase reactor keeps the polymerization reactions at a low level (since the polymerizable material is in a low amount in the medium) as well as the secondary reactions (such as the addition on the double bond of 1233xf). The addition of a gaseous compound may be advantageous for the reaction, which may be favored, for example, by the improvement of agitation (bubbling).

This gas may be inert such as nitrogen or helium or the gas may preferably be HCl. When HCl is used, the reaction is carried out despite the addition in the HCl medium, which is a reaction product.

Advantageously, this added gas is anhydrous chlortndric acid. The flow of the distillate gas is determined according to the operating conditions. For example, the flow of HCl, compared to the flow of starting product is such that the molar ratio Hcl: starting product is between 0.5: 1 and 5: 1, advantageously, between 1: 1 and 3: 1.

The liquid phase fluorination process according to the invention can be carried out continuously or semi-continuously. According to the preferred embodiment, the procedure is continuous.

The reactants (starting product and HF) and other compounds used in the reaction (chlorine, anhydrous HCl) can be fed into the reactor in the same place or in different places of the reactor. A preferred embodiment is when the gaseous compounds are injected into the bottom of the reactor, in particular, in order to enhance the mechanical separation and mixing.

If a recycle is used, it can be recycled directly at the reactor inlet or in a separate submerged pipe.

The reaction is carried out in a reactor dedicated to reactions involving halogens. Such reactors are known to the skilled worker, and may comprise coatings containing Hastelloy®, Inconel®, Monel® or fluoropolymers. The reactor may be equipped with means for heat transfer.

Figure 2 is a schematic representation of a method according to an embodiment of the invention. The reactor (equipped with a catalyst separation column, is not shown in the figure) for the liquid phase reaction is charged with catalyst, pentachloropropane and solvent. Next, pentachloropropane and HF are supplied continuously. An anhydrous HCl stream could also be injected.

The stream that is extracted from the reaction zone is in a gaseous form and mainly comprises 1233xf, HCl, HF as well as traces of solvent 122 separated if there are and other by-products including isomers 242 and possibly 243 (dichlorotrifluoroproan) especially 243db (1,1 , 1-trifluoro-2,3-dichloropropane). This stream is introduced into an HCl distillation column. A stream of HCl is extracted at the top of the column; at the bottom of the column a current containing 1233xf, 242, HF is extracted as traces of 122 and 243db. Typically, this tail current will comprise between 30 mol% and 70 mol% of 1233xf, between 30 mol% and 70 mol% of HF as well as smaller amounts, typically less than 10 mol%, preferably less than 5% in moles, of compounds of the series 242, 243 (especially 243db). This current is sent to a stage of separation by decantation. This decantation leads to two currents. The first stream comprises HF and soluble organic compounds and solvent, if any. This stream rich in HF is returned to the fluorination reaction. The second stream comprises 1233xf, 242, even an amount of HF as well as traces of 122 and 243db. This current is sent to a distillation column to separate theref. Traces of 122 and 243db are recovered at the bottom and are returned to the fluorination reactor. The 242 product (and generally the top saturated fluorinated products of the 240 series) will not accumulate since it is an intermediate product. At the top, a current containing HF and 1233xf is extracted. This head current can be further separated or sent directly to the next stage. Isomers 242 and / or 243db can be recycled in the process of the invention.

At the bottom of the liquid phase reactor, a stream containing the heavy materials is extracted. It is believed,

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without pretending to be limited, that the heavy materials comprise oligomers of the type C6F6H2CI2. The lower part of the fluorination reactor is purged with a flow and a frequency such that the accumulation of heavy materials is avoided (the purge ratio being defined by a flow and purge frequency that can be readily determined by the person skilled in the art). This current is treated in a column of recovery of heavy materials. These heavy materials are removed at the bottom of this column. A current containing HF, 122 and isomers 242 and 243db is recovered at the top of the column; This stream is recycled to the fluorination reactor.

EXAMPLES

The following examples illustrate the invention. The equipment used is described with reference to Figure 1. This consists of an autoclave with a 1 liter capacity jacket, made of 316L stainless steel, which is agitated using a magnetic stirrer. It is equipped with pressure and temperature indicators. The openings in the autoclave head allow the introduction of reactants and degassing. In the upper part it comprises a condenser as well as a valve to regulate the pressure. The condenser temperature is controlled using an independent thermostated bath.

The products of the reaction are continuously extracted during the reaction. These enter a scrubber that collects the HF and HCl hydrazides and then are cold trapped in liquid nitrogen. The weight gain of the washer and the trap make it possible to establish a mass balance.

At the end of the reaction period, the reaction medium is degassed to evacuate the residual HF. During this period of degassing, possibly extracted organic compounds are also trapped, always after having crossed the scrubber, which makes it possible to remove HF and HCl from the gas flow. In a final stage, the autoclave is opened and drained, a sample of the organic phase is analyzed after the catalyst has been hydrolyzed and extracted with a solution of chlorthophric acid.

The analysis is then carried out by gas phase chromatography on an expanded fluid sample. Chromatography analysis is carried out using a CP Sil 8 column, with dimensions 50m * 0.32mm * 5 | im. The oven temperature setting is as follows: 40 ° C for 10 min, then an elevation of 4 ° C / min until reaching 200 ° C.

Considering that xi is the initial amount of moles of raw material and xf is the total final amount of moles of raw material, the conversion (%) is: (xi-xf) / xi * 100. The selectivity of a product is calculated by the relationship between the amount of moles recovered from this product and the total amount of moles of the reaction products.

Examples 1 to 6 (not according to the invention).

0.5 moles of 240db or 1,1,1,2,3-pentachloropropane, 200 ml of anhydrous HF and 0.2 moles of catalyst are introduced into the autoclave. Next, HF is added continuously with a constant flow of 1 mol / h for 5 hours. The temperature is approximately 110 ° C and the absolute pressure is 9x105 Pa (9 bar). Different catalysts were investigated: SnCl4, SnCl4 doped with 0.03 moles of CsCl, TaCl5, TiCl4, SbCl5, liquid ionic methylmethylimidazolium combined with SbCl5 catalyst.

For Example 1, the 240db sample used contains 10.7% of isomer 240aa (1,1,2,2,3-pentachloropropane). Conversion is provided for each compound.

 Conversion Catalyst Selectivities (%)

 % 241 242 243db 1230x to 1233xf Xi

 Ex. 1

 SnCl4 240db: 76% 86.6 5.8 0 1.9 0 5.7

 240aa: 15%

 Ex 2

 SnCl4 + CsCl 44% 77.4 8.9 0.2 2.2 6.5 3.8

 Ex 3

 TaCl5 28% 88.4 0.2 0 0.4 0 11.0

From Example 4 to Example 6, the organic phase has not been analyzed since it was somewhat viscous. Only the analysis of the light fraction that could be collected is provided.

 Catalyst

 Ex 4

 TiCl4 3.2 g collected

 Molar composition: 54% 241, 1.5% 242, 32.8% 240db, 0% 1233xf

 Ex 5

 EmimCl + SbCl5 25 g collected

 Molar composition: 4.1% 241, 50% 242, 26.4% 243db, 0.7% 1233xf, 5.2% 240db

 Ex 6

 SbCl5 32.8 g collected

 Molar composition: 4.4% 241, 34.2% 242, 29.8% 243db, 0.5% 1233xf, 1.5% 240db

Thus ^ when the medium is an HF medium, substantially no conversion at 1233xf takes place.

Examples 7 and 8.

The same apparatus as in Examples 1 to 6 is used. 0.5 moles of 240db or 1,1,1,2,35 pentachloropropane and 0.2 moles of catalyst (0.2 moles of chloride) are introduced into the autoclave. ethylmethylimidazolium associated with 0.4 moles with SbCl5, providing 0.2 moles of fluorinated complex catalyst emim + Sb2Fn "emimCl). In one case, 151 g of F122 or 1,1,2-trichloro- are added in the autoclave 2,2-dichloroethane HF is added continuously with a constant flow of 1 mol / h for 5 hours The temperature is 133 ° C and the absolute pressure is 9x105 Pa (9 bar) The setpoint of the regulation of the condenser is always set at 90 ° C. In both 10 cases, HCl was flowed through the autoclave to improve the mixture and help separate the products.The molar ratio HCl at 240db is close to 2: 1.

 Example 7 Example 8

 F122

 - 151 g

 Conversion

 99.1% 99.7%

 Selectivity 1233xf (%)

 19.4 54.2

 Selectivity 242 (%)

 27.5 15.5

 Selectivity C6F6H2Cl2 * (%)

 2.9 4.2

 Others (%)

 43.6 18.1

 Total Mass Balance

 91.9% by weight 91% by weight

*: Structure of C6F6H2Cl2 identified by NMR as CF3-CCl = CH-CH = CCl-CF3

Therefore, 1233xf can be produced in substantial quantities. This is obtained in a medium that is not an acidic medium but an organic medium.

15 Examples 9 and 10.

The same apparatus is used as in the previous examples. 0.5 moles of raw material sample (240db or 240db with 10% of 240aa), 0.2 moles of catalyst (0.2 moles of ethylmethylimidazolium chloride associated with 0.4 moles with SbCl5, are introduced into the autoclave, or also represented as 0.2 moles of fluorinated complex catalyst emim + Sb2Fn "emimCl) and 2 moles of F122. HF is then added continuously with a flow

20 constant of 1 mol / h for 5 hours. The temperature is 135 ° C and the absolute pressure is 9x105 Pa (9 bar). The set point of the condenser regulation is always set at 90 ° C. For both cases, helium was flowed through the autoclave to improve the mixture and help drag the products. The flow of helium is 5 l / h.

 Example 10 Example 11

 Raw material

 240db with 10% 240aa 240db pure

 Conversion

 97.6% 99.8%

 143a (%)

 0.03 0.03

 1233xf (%)

 38.7 43.7

 1223xd (%)

 1.2 1.65

 1232xf (%)

 0.25 0.22

 243db (%)

 1.37 1.26

 233ab (%)

 0.65 3.95

 C6F6H2Cl2 * (%)

 2.81 2.77

 242 (%)

 34.5 29.6

 C6H4F4Cl4 (%)

 3.14 2.79

 Others (%)

 15.43 14.1

 Total Mass Balance

 91% by weight 93% by weight

Thus the preparation of 1233xf can take place either from pure 240db or from 240db containing 240aa isomer. Without intending to be limited, the applicant believes that the presence of intermediate 242 is an indicator that the reaction will occur, albeit at a slower rate, from 240aa in a similar way to when compared to 240db.

Examples 11 and 12.

In these examples, the reactants are continuously introduced through a liquid mass flow meter. As starting material between 100 and 200 ml of F122 or 1,1,2-trichloro-2,2-difluoroethane and 0.2 moles of catalyst (0.2 moles of ethylmethylimidazolium chloride associated with 0, are introduced into the autoclave. 4 moles with SbCl5, 10 providing 0.2 moles of fluorinated complex catalyst emim + Sb2Fn "). HF and 240db are then added continuously so that the molar ratio between HF and organic reactant is close to 8. The temperature is 130 -135 ° C and the absolute pressure is 8x105 Pa (8 bar) The set point of the condenser regulation is set at 90 ° C. In Example 11, no stabilizer is added to the organic reactant and in Example 12 add 100 ppm of p-methoxyphenol to compound 240db, thus investigating the impact of a stabilizer In both cases, HCl was flowed through the autoclave (approximately 0.1 mol / h) to improve the mixture and help separate the products. The molar ratio of HCl to 240db is close to 2: 1. The evolution of the composition Molar ion of the outlet gas over time is followed by GC analysis. The results show the benefit associated with the use of the stabilizer, as can be deduced from the amount of compound C6, in particular.

Example 11

 Weather

 Molar composition of the outlet gas (%)

 H

 122 1112a 244bb 1233xf 242 243db C6F6H2Cl2

 5

 65.3 9.6 4.5 18.0 0.004 0.9 0.006

 10.2

 51.9 7.3 4.6 31.9 0 3.1 0.007

 Weather

 Molar composition of the outlet gas (%)

 H

 122 1112a 244bb 1233xf 242 243db C6F6H2Cl2

 14.9

 45.6 9.8 4.6 38.9 0.008 0 0

 19.7

 41.9 4.3 3.1 39.4 0.02 10.2 0.001

 24.7

 29.3 3.1 2.7 43.1 0.2 19.5 0.04

 29.9

 6.7 0.9 3.2 57.7 7.3 14.8 2.7

 34.6

 1.6 0.2 2.6 66.4 8.5 10.1 3.3

 39.5

 0.6 0.1 3.9 57.9 12.5 10.5 5.2

 44.8

 0.2 0.03 3.1 61.0 13.4 8.0 5.1

 49.3

 0.1 0 1.9 65.6 11.4 6.8 4.9

 53.7

 0.2 0.03 2.1 61.8 14.9 5.7 5.4

 58.5

 0.1 0.01 1.6 63.6 14.5 5.6 4.9

 63.0

 0.04 0.01 1.2 60.2 18.8 3.7 5.5

 68.0

 0.02 0.005 1.2 60.6 18.8 3.2 5.3

 73.0

 0 0 1.5 51.7 23.7 3.9 6.0

 78.8

 0 0 1.7 40.6 29.8 6.4 6.6

 84.6

 0.096 0.02 2.1 46.6 25.1 6.9 5.4

 91.3

 0.145 0.02 1.6 52.6 19.5 5.5 4.6

 96.9

 0 0.02 2.8 21.8 28.9 20.2 6.8

 102.6

 0 0.01 3.8 33.6 24.3 16.8 5.7

 125.3

 0 0.03 3.3 20.9 26.9 25.3 6.1

 130.6

 0 0.03 4.2 19.7 15.9 43.8 3.8

Example 12

 Weather

 Molar composition of the outlet gas (%)

 H

 122 1112a 244bb 1233xf 242 243db C6F6H2Cl2

 5

 54.5 7.6 0.4 36.0 0.06 0.05 0.02

 10.2

 52.4 8.5 1.0 36.8 0.02 0.3 0

 Weather

 Molar composition of the outlet gas (%)

 15.8

 50.8 6.2 0.6 40.4 0.03 1.0 0.007

 22.4

 33.4 3.7 0.4 50.6 4.6 2.4 0.9

 38.6

 2.2 0.2 0.2 75.7 11.2 0.6 1.8

 45.6

 1.6 0.2 0.7 72.3 14.8 0.5 2.2

 62.5

 0.8 0.1 1.0 67.0 18.5 2.3 1.8

 68.7

 1.7 0.2 1.0 18.2 47.5 9.2 4.7

 85.6

 0.3 0.05 2.1 60.4 20.2 7.1 1.6

 91.5

 0.2 0.05 2.0 59.4 21.8 6.2 1.6

 97

 0.1 0.04 2.3 60.8 20.3 6.9 1.5

 113.4

 0.04 0.02 1.2 66.3 20.1 3.0 1.6

 120.1

 0.04 0.01 1.1 64.0 21.9 2.7 1.9

 138.9

 0 0 1.0 67.5 20.5 2.0 1.9

Example 13

100 ml of F122 or 1,1,2-trichloro-2,2-difluoroethane and 0.2 moles of catalyst (0.2 moles of ethylmethylimidazolium chloride associated with 0.4 moles are introduced into the autoclave as a starting material) SbCl5, providing 0.2 5 moles of fluorinated complex catalyst emim + Sb2Fn "). Then hF and 240db are added continuously with the

so that the molar ratio between HF and the organic reactant is close to 8. The 240db solution has first been diluted with 122 (400g of 122 per kg of 240db) so that both components are fed together to the reactor. It is fed together 122 in order to compensate for solvent separation during continuous operation. The temperature is 130-135 ° C and the absolute pressure is 8x105Pa (8 bar). The set point of the 10 capacitor regulation is set at 90 ° C. HCl flows through the autoclave (approximately 0.1 mol / h) to

improve the mix and help separate the products. The molar ratio of HCl at 240db is close to 2: 1. The evolution of the molar composition of the outlet gas over time is followed by GC analysis.

Example 13

 Weather

 Molar composition of the outlet gas (%)

 h

 122 1112a 244bb 1233xf 242 243db C6F6H2Cl2

 6.5

 52.4 2.5 0.9 42.0 0.39 0.1 0.03

 29.5

 55.9 2.8 1.1 36.8 0.28 1.2 0.03

 46.7

 41.7 2.2 0.5 46.3 4.2 0.9 0.7

 53.4

 36.2 2.2 0.5 47.3 7.6 0.7 1.6

 69.9

 33.3 1.3 0.6 49.0 9.9 0.9 2.0

 76.5

 31.85 1.4 0.7 46.1 12.9 1.4 2.5

 Weather

 Molar composition of the outlet gas (%)

 h

 122 1112a 244bb 1233xf 242 243db C6F6H2Cl2

 93.8

 30.3 1.3 1.2 40.3 16.6 3.9 2.9

 99.8

 30.72 1.3 1.6 40.2 15.3 4.9 2.7

 122.4

 40.1 1.8 1.7 35.2 10.9 6.0 1.4

 127.9

 36.6 1.9 1.2 38.6 10.6 6.3 1.6

 145.4

 27.3 1.4 0.7 51.6 11.5 2.1 1.8

 151.9

 27.3 1.5 0.7 48.9 13.4 1.9 2.1

 168.9

 27.0 1.4 0.7 50.5 12.6 1.5 2.1

 175.4

 27.6 1.5 0.7 50.2 12.2 1.5 1.9

 192.8

 27.1 1.3 0.8 50.2 12.9 1.5 2.2

 199.1

 27.9 1.3 0.9 52.4 10.3 1.6 1.6

 216.0

 27.4 1.3 0.9 50.4 12.1 1.6 2.1

Claims (21)

5 10 fifteen twenty 25 30 35 40 Four. Five 1. Process of catalytic fluorination in Kquida phase in an organic product medium 1,1,1,2,3-pentachloropropane or a mixture of 1,1,1,2,3-pentachloropropane and 1,1,2,2 , 3-pentachloropropane, in 2-chloro-3,3,3-trifluoropropene in the presence of a catalyst that is an ionic liquid, said process being carried out in a solvent. 2. Method according to claim 1, wherein the solvent is present in an amount for a dilution ratio of at least 20%. 3. Method according to claim 1 or 2, wherein the solvent is selected from 1,2-dichloroethane, 1,2,3-trichloropropane, 1-chloro-1-fluoroethane, 1,1-difluoroethane, 1,1-dichloroethane and 1,3-dichloro-1-fluorobutane, isomers of tetrachlorofluoropropane, isomers of trichlorodifluoropropane and isomers of dichlorotrifluoropropane, 1,1,1,3,3-pentafluorobutane and 1,1,2-trichloro-2,2-difluoroethane, solvents nitrates including nitromethane and nitrobenzene, sulfones including tetramethylene sulfone and dimethylsulfone, 1,1,2-trichloro-2-fluoroethane or perchlorethylene, or mixtures thereof. 4. Method according to any one of claims 1 to 3, wherein the molar ratio of catalyst / organic compounds is between 2 mol% and 90 mol%. 5. Method according to one of claims 1 to 4 wherein chlorine is added during the reaction. 6. Method according to one of claims 1 to 5, wherein a gas is injected. 7. Method according to claim 6, wherein the gas flow, compared to the flow of the starting product, is between 0.5: 1 and 5: 1. 8. Method according to one of claims 1 to 7, wherein the reaction product is extracted in a gaseous state. 9. The method according to one of claims 1 to 8, wherein 1,1,1,2,2-pentachloropropane contains up to 20 mol% of the 1,1,2,2,3-pentachloropropane isomer. 10. Method according to one of claims 1 to 9, wherein the reaction temperature ranges between 30 ° C and 200 ° C. 11. Method according to one of claims 1 to 10, wherein the reaction pressure is greater than 2x105 Pa (2 bar). 12. Method according to one of claims 1 to 11, wherein the molar ratio of HF: starting compound is between 0.5: 1 and 50: 1. 13. Method according to one of claims 1 to 12, carried out in the presence of a stabilizer selected from the group consisting of p-methoxyphenol, t-amylphenol, thymol, limonene, d, l-limonene, quinones, hydroquinones, epoxides, Amines and their mixtures. 14. Method according to claim 13, wherein the stabilizer is used in an amount of 5-1000 ppm. 15. Method according to one of claims 1 to 14, comprising: (i) contacting 1,1,1,2,3-pentachloropropane or a mixture of 1,1,1,2,3-pentachloropropane and 1,1,2,2,3-pentachloropropane with hydrogen fluoride in a liquid phase in an organic medium under conditions sufficient to form a reaction mixture comprising 2-chloro-3,3,3-trifluoropropene; (ii) separating the reaction mixture into a first stream comprising HCl, and a second stream comprising HF and 2-chloro-3,3,3-trifluoropropene. 16. The method according to claim 15, wherein the second stream comprises between 30 mol% and 70 mol% of 1233xf (2-chloro-3,3,3-trifluoropropene), between 30 mol% and 70 mol% of HF and less than 10 mol%. 17. Method according to claim 15 or 16, wherein step (ii) is a distillation stage. 18. Method according to one of claims 15 to 17, wherein the second stream is further separated. 19. Method according to claim 18, wherein the organic current is further purified. 20. Method according to one of claims 15 to 19, further comprising a purge stage for extracting the heavy materials formed during step (i). 21. Method according to any one of the preceding claims, carried out continuously.