JP6360084B2 - Process for producing 2-chloro-1,1,1,2-tetrafluoropropene by liquid phase fluorination of 2-chloro-3,3,3-trifluoropropene - Google Patents

Description

The present invention provides the product 2-chloro-1,1,1,2-tetrafluoropropane (HCF C 244bb) by liquid phase catalytic fluorination of 2-chloro-3,3,3-trifluoropropene (HCFO1233xf). It relates to a method of manufacturing.

  The use of chlorofluorocarbons (CFCs) was prohibited by the Montreal protocol for ozone layer protection. Instead of chlorofluorocarbons, compounds that have less impact on the ozone layer, such as hydrofluorocarbons, HFCs, such as HFC-134a, have come to be used. However, these compounds become greenhouse gases. Accordingly, there is a need to develop one with low ODE (ozone depletion potential) and low GWP (global warming potential). Hydrofluorocarbons (HFCs) have been identified as important candidates for compounds that do not affect the ozone layer, but there is still a need to find compounds that exhibit relatively high GWP values and even lower GWP values. Yes. Hydrofluoroolefins (HFO) are considered to be an alternative with very low ODE and GWP values.

  Several methods for producing this HFO compound, particularly propylene, have been developed. Compound 244bb (2-chloro-1,1,1,2-tetrafluoropropane) is particularly desired as an intermediate in the production of 1234yf (2,3,3,3-tetrafluoropropene).

  Patent Document 1 describes a method for synthesizing 244bb from 1233xf (2-chloro-3,3,3-trifluoropropene by liquid phase fluorination or gas phase fluorination. 87% by liquid fluorination. Although the yield is stated, only overhead gas is considered and the liquid phase remaining in the reactor is not analyzed.

Patent Documents 2 to 6 disclose a method for producing 244bb starting from 1233xf. In all these documents, SbCl ₅ is used as the catalyst. A high selectivity of up to 90% has been reported. Implementation of the use of additives or mixing the catalyst SbCl ₃ / SbC1 ₅ of HC1 into the liquid phase reactor is not stated.

    Patent Document 7 describes an example in which 1233xf is used as a raw material for producing 244bb by liquid phase fluorination. The yield of 244bb is between 87-89%.

  The key factor for this reaction is selectivity. In fact, unreacted feeds are easy to recycle, and there is no use for by-products and reaction products, especially chlorinated products in industrial processes, so high selectivity allows low conversion. It is.

International Patent Publication No. W02007 / 079431 US Patent Publication No. US2009 / 0182179 US Patent Publication No. US2009 / 0240090 US Patent Publication No. US2009 / 0312585 US Patent Publication No. US2010 / 0036179 International Patent Publication No. WO2009 / 137658

  Accordingly, there is a need for a process for producing compound 244bb with high selectivity.

  The present invention relates to the product 2-chloro-1,1,1,2-tetrafluoropropane by catalytic fluorination of the product 2-chloro-3,3,3-trifluoropropene (HCFO 1233xf) in the liquid phase in the presence of a catalyst. A method of manufacturing the same is provided.

Here is an example:
(1) The ionic liquid comprises at least one halogenated or oxyhalogenated Lewis acid based on aluminum, titanium, niobium, tantalum, tin, antimony, nickel, zinc or iron, and a general formula: Y ⁺ A ⁻ Wherein A ⁻ represents a halide anion or a hexafluoroantimonate anion, and Y ⁺ represents a quaternary ammonium cation, a quaternary phosphonium cation or a tertiary sulfonium cation. fluorinated complex catalyst emim ⁺ Sb ₂ F ₁₁ ^- a is preferably.
(2) The process of the present invention is carried out in a catalyst-etched phase, preferably with a catalyst / organic molar ratio of 50 mol% or more.
(3) During the reaction, 0.05 to 20 mol%, preferably 1 to 17 mol% of chlorine is added in a molar ratio per mol of the starting compound.
(4) A gas, preferably a noble gas, preferably nitrogen or helium, is injected and the ratio of the gas flow compared to the starting product flow is 0.5: 1 to 5: 1, preferably 1: 1 to 3. : 1.
(5) The reaction product is extracted with gas.
(6) The reaction temperature is between 30 ° C and 200 ° C, preferably between 40 ° C and 170 ° C, advantageously between 50 ° C and 150 ° C.
(7) The reaction pressure is at least 2 bar, preferably between 4 and 50 bar, in particular between 5 and 15 bar.
(8) The molar ratio of HF: starting compound is between 0.5: 1 and 50: 1, preferably between 3: 1 and 20: 1, more preferably between 5: 1 and 15: 1.

In general, the method of the present invention comprises the following steps (i) to (iv):
(I) Conditions sufficient to form 2-chloro-3,3,3-trifluoropropene to form a reaction product (reaction mixture) containing 2-chloro-1,1,1,2-tetrafluoropropane Under contact with hydrogen fluoride in the presence of an ionic liquid-based catalyst in the liquid phase,
(Ii) separating the HC1 and HF from the reaction product to form an organic mixture in the separation process,
(Iii) This organic mixture is divided into a first stream consisting of 2-chloro-1,1,1,2-tetrafluoropropane and a second stream consisting of unreacted 2-chloro-3,3,3-trifluoropropene. And separated into
(Iv) Recycle unreacted 2-chloro-3,3,3-trifluoropropene to step (i).

In particular,
11:26 2016/01/14 (ii) can separate HCl by distillation, HF can be separated by decantation or washing process,
Stage (iii) can be an extractive distillation stage or a separation process using a membrane, or the organic mixture can be fed into a dehydrochlorination reaction to give 2-chloro-1,1,1,2-tetrafluoropropane. Instead of 1,1,1,2-tetrafluoropropene, the product obtained can be separated from 2-chloro-3.3.3-trifluoropropene.

  The method of the present invention is preferably carried out by a continuous method.

The present invention further provides a process for producing 2,3,3,3-tetrafluoropropene comprising the following steps:
(I) making 2-chloro-1,1,1,2-tetrafluoropropane by the above method of the present invention;
(Ii) The above 2-chloro-1,1,1,2-tetrafluoropropane is dehydrochlorinated to 2,3,3,3-tetrafluoropropene.

  The invention further relates to the product obtained at the above stage of the process according to the invention, in particular a mixture comprising mainly 244bb and impurities and / or unreacted starting materials and / or by-products.

  The present invention is based on the discovery that liquid ionic base catalysts have a positive impact on the selectivity of 244bb in a 1233xf liquid phase fluorination reaction. From an industrial point of view, selectivity is more important than conversion. That is, the unreacted product can be recycled (if the conversion is low), but compounds that cannot be further chemically modified (if the selectivity is low) are an obvious loss.

Liquid ion-based catalysts are described in, for example, Patent Document 7 (particularly, page 4, line 1 to page 6, line 1), patent document 8 of the present applicant, and non-patent document 1. Yes.
International Patent Publication No. W02008 / 149011 International Patent Publication No. W001 / 81353 "Liquid-phase HF Fluorination", Multiphase Homogeneous Catalysis, Ed. Wiley-VCH, (2002), 535

  Suitable catalysts are derivatives of Lewis acids based on aluminum, titanium, niobium, tantalum, tin, antimony, nickel, zinc or iron. The ionic liquid is a non-aqueous salt having an ionic characteristic that is a liquid at a particularly moderate temperature (preferably a temperature of 120 ° C. or less).

Catalysts based on ionic liquids are at least one halogenated or oxyhalogenated Lewis acid based on aluminum, titanium, niobium, tantalum, tin, antimony, nickel, zinc or iron and the general formula: Y ⁺ It is preferably obtained by reaction of A ^-with a salt. Where A ⁻ is a halide (bromide, iodide, preferably chloride or fluoride) anion or hexafluoroantimonate (SbF 6 ⁻ ) anion, and Y ⁺ is a quaternary ammonium cation, quaternary phosphonium. Cation or tertiary sulfonium cation.

Pentachloride, antimony and ethyl - methyl - imidazolium chloride is the reaction product of a ride Compound fluorinated complex catalyst emim ⁺ Sb ₂ F ₁₁ ^- antimony-based ionic liquids, such as the preferred catalyst.

  The reaction condition (particularly pressure) is the pressure at which the reactant becomes liquid. In one embodiment of the invention, the reaction product is a gas and the reactant is a liquid. The fact that the reaction product is a gas means that it can be recovered in the gas phase at the outlet of the reaction zone. The reaction temperature is therefore between 30 ° C. and 200 ° C., preferably between 40 ° C. and 170 ° C., advantageously between 50 ° C. and 150 ° C. The reaction pressure is generally at least 2 bar, preferably between 4 and 50 bar, in particular between 5 and 15 bar.

  The molar ratio of HF: starting compound is generally between 0.5: 1 and 50: 1, preferably between 3: 1 and 20: 1, advantageously between 5: 1 and 15: 1. Other reaction conditions, in particular the flow rate, can be determined by those skilled in the art according to ordinary general knowledge according to temperature, pressure, catalyst, reactant ratio and the like. Care is taken to achieve the highest selectivity.

Although not a preferred embodiment, a solvent can be used. This solvent is an organic solvent which is inert under the reaction conditions. This solvent is generally a saturated C2-C6 solvent to avoid addition reactions. This type of solvent is described in Patent Document 9, for example.
French Patent Publication No. FR 2733227

  This solvent has a boiling point (under atmospheric pressure) of, for example, 40 ° C. or higher, preferably 50 ° C. or higher, in particular 60 ° C. or higher. When the reaction temperature is high, the pressure is higher, and the boiling point of the solvent under the reaction conditions is higher than the temperature used in the reaction.

  Although it is possible to operate with various catalyst / organic ratios, a catalyst rich phase is generally preferred. The molar ratio of catalyst / organic matter is preferably 50 mol% or more, for example. The starting medium is preferably a pure catalyst.

  Chlorine streams can be used to extend catalyst life. In general, 0.05 to 20 mol%, preferably 1 to 17 mol% of chlorine is mixed per 1 mol of starting material 1233xf. Chlorine can be introduced in the form of pure chlorine or mixed with a noble gas (eg nitrogen or helium). A small amount of chlorine can be used by using an ion catalyst.

  Starting material stabilizers can be used as needed. The amount is generally 5 to 1000 ppm, preferably 10 to 500 ppm. Examples of stabilizers are p-methoxyphenol, t-amylphenol, thymol, limonene, d, l-limonene, quinones, hydroquinone derivatives, epoxides, amines and mixtures thereof.

  The counterproduct can also be stripped using a stripping gas and mechanically removed. It is advantageous to remove gaseous 244bb from the liquid phase reactor (less side reactions). Further, the addition of a gaseous compound is advantageous for the reaction, and is preferable because, for example, stirring (bubbling) is improved. This gas can be an inert gas such as nitrogen or helium. This gas is preferably different from HC1. In general, the ratio of gas flow compared to the starting material is between 0.5: 1 and 5: 1, preferably between 1: 1 and 3: 1.

  The liquid phase fluorination process of the present invention can be carried out in a continuous or semi-continuous process. The preferred embodiment process is a continuous process. The reactants (starting material and HF) and other compounds used in the reaction (chlorine, noble gases) can be supplied at the same location in the reactor or at different locations in the reactor. In a preferred embodiment, gaseous compounds are injected from the bottom of the reactor to improve mechanical stripping and agitation.

  If recirculated, it can be returned directly to the reactor inlet or returned to another dip pipe.

  The reaction is carried out in a reaction apparatus for reaction containing halogen. This type of reactor is known to those skilled in the art and can have a coating comprising Hastelloy®, Inconel®, Monel® or a fluoropolymer. The reactor can be equipped with heat transfer means.

  The specific process of the present invention is generally performed as follows. An ionic liquid-based catalyst is placed in a reactor for a liquid phase reaction (eg, equipped with a catalyst strip column). Next, 1233xf and HF are continuously supplied. A rare gas or anhydrous chlorine stream can also be injected. The stream withdrawn from the reaction zone is in the form of a gas and mainly comprises 244bb, 240 series isomerism (241 + 242 + 243), chlorine and rare gases, unreacted 1233xf, and HF. 244bb is separated from this stream and other compounds (1233xf, HF and 240 series isomers) are recycled to the reactor.

  1244yf is made using 244bb produced according to the method of the present invention. The process for producing 1234yf starting from 244bb is known and uses a dehydrochlorination catalyst. This reaction is preferably carried out in the gas phase as is known to those skilled in the art. The dehydrochlorination catalyst can be a metal halide, a metal halide oxide, a neutral (or zero oxidation state) metal or metal alloy, as well as a bulk or supported activated carbon.

Regarding the reaction from 244bb to 1234yf, the following documents can be referred to.
US Patent Publication No. US2009 / 0182179 US Patent Publication No. US2009 / 0240090 US Patent Publication No. US2009 / 0312585 US Patent Publication No. US2010 / 0036179 US Patent Publication No.

These contents form part of the present invention. This reaction is known to those skilled in the art.
Examples of the present invention will be described below, but the present invention is not limited to the following examples.

A 1 liter autoclave made of stainless steel 316L with jacket, equipped with a magnetic stirrer and equipped with a pressure gauge and a thermometer was used. Reactants can be introduced and degassed through the holes in the head of the autoclave and have a pressure control valve and a condenser at the top. The condenser is temperature controlled using an independent thermostat bath.
During the reaction, the reaction product is continuously taken out and placed in a scrubber to recover HF and HC1 and trapped in liquid nitrogen. Calculate the mass balance from the increase in scrubber weight and trap volume.

  At the end of the reaction period, the reaction medium is degassed and the residual HF is evacuated. Organics that would be withdrawn simultaneously during this degassing are trapped after always passing through a scrubber to remove HF and HC1 from the gas stream. In the last stage, the autoclave is opened and discharged, and after the catalyst is hydrolyzed and extracted with hydrochloric acid solution, a sample of the organic phase is analyzed.

  The liquid sample was then analyzed by gas phase chromatography. Chromatographic analysis was performed using column CP Sil8 (dimensions 50 m, 0.32 mm, 5 μm). The furnace temperature was programmed for 10 minutes at 40 ° C. and then 200 ° C. with a 4 ° C./min ramp. The conversion (%) is (xi−xf) / xi * 100 where xi is the initial molar amount of the material and xf is the total molar yield of the material. Product selectivity is calculated from the sum and ratio of the recovered molar amount of product and the molar amount of product reacted.

Example 1 (Comparative Example)
Placed in a reactor to SBC1 ₅ catalyst 150 ml, 2 h of anhydrous HF flow at 60 ° C., it was fluorinated by introducing. The HF stream was added at a 5: 1 molar ratio to the amount of catalyst. In addition, chlorine was added continuously to maintain antimony oxidation at a high level. A chlorine stream was fed at 1 g / hr during the experiment during the perfluorination stage (conversion stage, 15%).

  After this perfluorination step, 0.5 mole of 1233xf was introduced into the reactor. The temperature was adjusted to 85 ° C. During the experiment, anhydrous HF was flowed at a flow rate of 1 mol / hour for 5 hours. The pressure was 8 bar. The condenser set point was 90 ° C. (meaning no reflux to the reactor). Helium was allowed to flow at a flow rate of 3.4 N1 / h through the reactor deep tube (ratio 1.5).

  After 5 hours, the pressure was reduced and the reactor was heated to remove residual HF. When the reactor was opened, 289 g of catalyst remained at the bottom. During the experiment, organic substances and reactants were collected in a cold trap. The results of conversion and selectivity are shown in [Table 1].

Example 2 (Invention)
And SbCl ₅ in 100 ml, fluorination of 50m1 complex catalyst emim ⁺ Sb2F11 ^- become ethyl - introducing a methyl imidazolium chloride compound into the reactor, it was fluorinated by flowing 2 hours anhydrous HF at 60 ° C.. The HF stream was added at a 5: 1 molar ratio to the amount of catalyst. In addition, chlorine was continuously added to increase the oxidation level of antimony. During the experiment, a chlorine stream was fed at lg / hour during the perfluorination stage. The conditions of Example 1 were applied. The results are shown in [Table 1].

Although a significant amount of unknown compound is present in the comparative example, it can be seen that the level is lowered in the present invention (9.1 vs. 2.6). In addition, 1223xd (CF ₃ —CCl═CHC 1 ) and 233ab (CF ₃ —CCl ₂ —CHCl) are chlorinated by-products, which are large in the comparative example, but small in the present invention. It is at a low level (1.3 + 4.5 = 5.8 vs. 0.06 + 0.5 = 0.56). In the comparative example, 14.9% of unnecessary by-products can be formed, but in the present invention, it is 3.2% or less, and the difference is about 12%, which is a very significant difference. Therefore, the selectivity of the present invention is very high and can be re-purified and easy.

Claims (17)

The following (i) to (iv):
(I) liquid 2-chloro-3,3,3-trifluoropropene under conditions sufficient to form a reaction product comprising 2-chloro-1,1,1,2-tetrafluoropropane. Contacting with hydrogen fluoride in the presence of an ionic liquid-based catalyst in the phase;
(Ii) separating HCl and HF from the reaction product in a separation process to form an organic mixture;
(Iii) This organic mixture is divided into a first stream consisting of 2-chloro-1,1,1,2-tetrafluoropropane and a second stream consisting of unreacted 2-chloro-3,3,3-trifluoropropene. And separated into
(Iv) recycling unreacted 2-chloro-3,3,3-trifluoropropene to step (i);
Has steps,
In step (i), an inert gas is introduced, the reaction product is removed in the gaseous state, and in step (ii) HCl is separated by distillation,
The catalyst and the Lewis acid halogenated at least one was based on antimony general formula: Y ⁺ A ^- salt (A ^- represents an anion of anion or hexafluoroantimonate halide, Y ⁺ is Obtained by reaction with quaternary ammonium cations)
A catalytic fluorination method characterized by the above. The process according to claim 1 , wherein the process is carried out in a catalyst rich phase. The process according to claim 2 , wherein the catalyst / organic molar ratio is 50 mol% or more. The process according to any one of claims 1 to 3 , wherein 0.05 to 20 mol% of chlorine is added during the reaction in a molar ratio per mol of the starting compound. Process according to claim 4 , wherein 1 to 17 mol% of chlorine is added during the reaction in a molar ratio per mol of starting compound. The method according to any one of claims 1 to 5 , wherein the inert gas is nitrogen or helium. 7. A process according to claim 6 , wherein the ratio of the inert gas stream compared to the starting compound stream is 0.5: 1 to 5: 1. 8. A process according to claim 7 , wherein the ratio of the inert gas flow compared to the starting compound flow is 1: 1 to 3: 1. The method according to any one of claims 1 to 8 , wherein the reaction temperature is between 30C and 200C. The process according to claim 9 , wherein the reaction temperature is between 50C and 150C. The method according to any one of claims 1 to 10 , wherein the reaction pressure is 2 bar or more. 12. Process according to claim 11 , wherein the pressure of the reaction is between 5 and 15 bar.   13. A process according to any one of the preceding claims wherein the HF: starting compound molar ratio is between 0.5: 1 and 50: 1. 14. The process of claim 13 , wherein the molar ratio of HF: starting compound is between 5: 1 and 15: 1. The method according to any one of claims 1 to 14 for a continuous process. The 2-chloro-1,1,1,2-tetrafluoropropane prepared using the method according to any one of claims 1 to 15 is further dehydrochlorinated to produce 2,3,3,3-tetra The method according to any one of claims 1 to 15 , wherein the method is fluoropropene. The process according to claim 16 , wherein the dehydrochlorination is carried out in the gas phase.