Process for the production of 1-chloro-3,3,3-trifluoropropene

Abstract

The present invention relates to a process for producing 1-chloro-3,3,3-trifluoropropene. The present invention relates to a process for producing 1-chloro-3,3,3-trifluoropropene comprising a step i) of contacting in a reactor hydrofluoric acid (HF) and a starting composition comprising at least one chlorinated compound selected from 1,1,3,3-tetrachloropropene (1230za), 1,3,3,3-tetrachloropropene (1230zd) or 1,1,1,3,3-pentachloropropane (240fa) or mixtures thereof to produce a stream A comprising 1-chloro-3,3,3-trifluoropropene (1233zd), characterized in that said step i) is carried out in a liquid phase poor in HF.

Description

[0001] This application is a divisional application of patent application No. 201980030905.4, filed on May 13, 2019, entitled "Method for producing 1-chloro-3,3,3-trifluoropropylene". Technical Field

[0002] This invention relates to the production of hydrochlorofluoroolefins. More particularly, this invention relates to the production of 1-chloro-3,3,3-trifluoropropylene. Background Technology

[0003] 3,3,3-Trifluoro-1-chloropropene, or alternatively 1-chloro-3,3,3-trifluoropropene (HCFO-1233zd), exists in two isomers: the cis isomer, namely Z-3,3,3-trifluoro-1-chloropropene (HCFO-1233zdZ), and the trans isomer, namely E-3,3,3-trifluoro-1-chloropropene (HCFO-1233zdE). They have different boiling points, specifically 18.5 °C for the trans compound and 39.5 °C for the cis compound.

[0004] E-3,3,3-trifluoro-1-chloropropene (HCFO-1233zdE)-based fluids have been found to have a variety of applications in various industrial sectors, particularly as heat transfer fluids, propellants, foaming agents, gaseous dielectrics, monomer or polymeric media, carrier fluids, abrasives, desiccants, and fluids used in energy production units.

[0005] The production of HCFO-1233zdE is accompanied by many byproducts with boiling points close to HCFO-1233zdE. This makes purification procedures relatively complex and expensive. Difficulties encountered during the purification of HCFO-1233zdE often result in considerable loss of the target product. Furthermore, the byproducts can form azeotropic compositions with HCFO-1233zdE, making separation by simple distillation difficult or even impossible.

[0006] A method for preparing HCFO-1233zdE from 1,1,3,3-tetrachloropropene in the absence of a catalyst and in the liquid phase is known by US 5,877,359. The HF / 1230za molar ratio in the fluorination reactor is 12 to 500. A method for fluorinating 1,1,3,3-tetrachloropropene in the absence of a catalyst and in the liquid phase is also known by US 9,643,903. For obvious environmental and safety reasons, the presence of significant amounts of HF under pressure during industrial reactor start-up or at steady-state conditions is undesirable. Concern for new, environmentally conscious processes constitutes part of ongoing process improvements.

[0007] Furthermore, a significant amount of overfluorination byproducts was observed in association with the presence of substantial amounts of this HF. The presence of 245fa can lead to yield losses, as this mixture is known to form an azeotropic mixture with the major product 1233zdE (see US2017 / 174965 in particular). Therefore, it is difficult to separate and must be removed as an azeotropic mixture, resulting in yield losses.

[0008] Therefore, a new method is needed to minimize the above-mentioned drawbacks. Summary of the Invention

[0009] According to a first aspect, the present invention provides a method for producing 1-chloro-3,3,3-trifluoropropene, comprising step i) contacting hydrofluoric acid (HF) with a starting composition in a reactor to produce a stream A comprising 1-chloro-3,3,3-trifluoropropene (1233zd), said starting composition comprising at least one chlorine compound selected from 1,1,3,3-tetrachloropropene (1230za), 1,3,3,3-tetrachloropropene (1230zd) and 1,1,1,3,3-pentachloropropane (240fa) or mixtures thereof, characterized in that step i) is carried out in a low-HF liquid phase.

[0010] Reducing the amount of HF in the fluorination reactor tends to protect the reactor from corrosion. Furthermore, reducing the amount of HF in the reactor improves operational reliability, making the method easily adaptable to industrial scale. Therefore, the risk of decantation in the liquid phase is minimized. Additionally, the method according to the invention reduces the amount of co-products of over-fluorination.

[0011] According to a preferred embodiment, the low-HF liquid phase is a liquid phase containing less than 15% by weight of HF, advantageously less than 10% by weight of HF, preferably less than 8% by weight of HF, more preferably less than 6% by weight of HF, particularly less than 5% by weight of HF, even more particularly less than 4% by weight of HF, preferably less than 2% by weight of HF, based on the total weight of the liquid phase.

[0012] According to a preferred embodiment, the at least one chlorine compound is 1,1,3,3-tetrachloropropene (1230za).

[0013] According to a preferred embodiment, the starting composition comprises at least 10% by weight of the at least one chlorine compound, based on the total weight of the starting composition.

[0014] According to a preferred embodiment, the starting composition contains less than 10% by weight of HF, based on the total weight of the starting composition.

[0015] According to a preferred embodiment, the liquid phase comprises at least 10% by weight of formula (I)C3H n F m Cl p (I) compounds, where n is an integer from 0 to 8, m is an integer from 0 to 8, and p is an integer from 0 to 8.

[0016] According to a preferred embodiment, step i) is performed in the absence of a catalyst.

[0017] According to a preferred embodiment, stream A comprises a co-product selected from 1,3,3,3-tetrafluoropropylene and 1,1,1,3,3-pentafluoropropane.

[0018] According to a preferred embodiment, the amount of the co-product selected from 1,3,3,3-tetrafluoropropylene and 1,1,1,3,3-pentafluoropropane is less than 0.5% by weight, based on the total weight of stream A at the reactor outlet.

[0019] According to a preferred embodiment, step i) is performed at a temperature of 50°C to 150°C.

[0020] According to a preferred embodiment, step i) is performed under a pressure of 5 to 20 bara.

[0021] According to a second aspect, the present invention provides a composition comprising at least 98 mol% of (E / Z)-1-chloro-3,3,3-trifluoropropene and less than 0.5 mol% of a co-product selected from 1,3,3,3-tetrafluoropropene and 1,1,1,3,3-pentafluoropropane.

[0022] According to a preferred embodiment, the composition comprises at least 99.5 mol% of (E / Z)-1-chloro-3,3,3-trifluoropropene, less than 0.3 mol% of 1,3,3,3-tetrafluoropropene, and less than 0.05 mol% of 1,1,1,3,3-pentafluoropropane.

[0023] According to a preferred embodiment, the composition is obtained at the outlet of a reactor carrying out the method according to the invention. Detailed Implementation

[0024] According to a first aspect of the invention, a method for producing 1-chloro-3,3,3-trifluoropropene is provided. The method includes step i) of contacting hydrofluoric acid (HF) with a starting composition in a reactor to produce a stream A comprising 1-chloro-3,3,3-trifluoropropene (1233zd), said starting composition comprising at least one chlorine compound selected from 1,1,3,3-tetrachloropropene (1230za), 1,3,3,3-tetrachloropropene (1230zd), and 1,1,1,3,3-pentachloropropane (240fa), or mixtures thereof. Step i) is preferably carried out in a low-HF liquid phase.

[0025] As mentioned above, the method of the present invention enables the production of 1-chloro-3,3,3-trifluoropropene in high yield and with high selectivity. Compared with methods carried out in HF-rich media, the amount of co-products in the final reaction mixture is significantly reduced when the method of the present invention is carried out in a low-HF medium. The present invention thus provides a more efficient method.

[0026] According to a preferred embodiment, the starting composition comprises at least 10% by weight of the at least one chlorine compound, based on the total weight of the starting composition. The starting composition advantageously comprises at least 15% by weight of the at least one chlorine compound, preferably at least 20% by weight, more preferably at least 25% by weight, particularly at least 30% by weight, even more particularly at least 35% by weight, preferably at least 40% by weight, advantageously preferably at least 45% by weight, preferably at least 50% by weight, and particularly preferably at least 55% by weight, based on the total weight of the starting composition.

[0027] The starting composition preferably contains at least 60% by weight or at least 65% by weight or at least 70% by weight or at least 75% by weight or at least 80% by weight or at least 85% by weight or at least 90% by weight or at least 95% by weight or at least 99% by weight of the at least one chlorine compound, based on the total weight of the starting composition.

[0028] The method according to the invention is efficient if the starting composition contains one of the at least one chlorine compound in high purity or a mixture of the at least one chlorine compound with other organic compounds.

[0029] According to a preferred embodiment, the at least one chlorinated compound is 1,1,3,3-tetrachloropropene (1230za). The method therefore includes step i) of contacting hydrofluoric acid (HF) with a starting composition in a reactor to produce a stream A containing 1-chloro-3,3,3-trifluoropropene (1233zd), the starting composition comprising 1,1,3,3-tetrachloropropene (1230za); as defined above, step i) is carried out in a low-HF liquid phase. Preferably, the method of the invention enables the production of 1-chloro-3,3,3-trifluoropropene in the form of a mixture of cis and trans isomers. The method of the invention enables the production of the trans-1-chloro-3,3,3-trifluoropropene isomer in a predominantly dominant form, preferably at least 90 mol% of the trans isomer.

[0030] The starting composition therefore comprises at least 10 wt% of 1,1,3,3-tetrachloropropene, based on the total weight of the starting composition. The starting composition advantageously comprises at least 15 wt% of 1,1,3,3-tetrachloropropene, preferably at least 20 wt% of 1,1,3,3-tetrachloropropene, more preferably at least 25 wt% of 1,1,3,3-tetrachloropropene, particularly at least 30 wt% of 1,1,3,3-tetrachloropropene, even more particularly at least 35 wt% of 1,1,3,3-tetrachloropropene, preferably at least 40 wt% of 1,1,3,3-tetrachloropropene, advantageously preferably at least 45 wt% of 1,1,3,3-tetrachloropropene, preferably preferably at least 50 wt% of 1,1,3,3-tetrachloropropene, particularly preferably at least 55 wt% of 1,1,3,3-tetrachloropropene, based on the total weight of the starting composition.

[0031] The starting composition preferably contains at least 60 wt% or at least 65 wt% or at least 70 wt% or at least 75 wt% or at least 80 wt% or at least 85 wt% or at least 90 wt% or at least 95 wt% or at least 99 wt% of 1,1,3,3-tetrachloropropylene, based on the total weight of the starting composition.

[0032] According to a preferred embodiment, the starting composition contains less than 15% by weight of HF, advantageously less than 10% by weight of HF, preferably less than 8% by weight of HF, more preferably less than 6% by weight of HF, particularly less than 5% by weight of HF, even more particularly less than 4% by weight of HF, and preferably less than 2% by weight of HF, based on the total weight of the starting composition.

[0033] Preferably, in the method of the present invention, the starting composition is free of HF. The term "free of" means less than 500 ppm, preferably less than 100 ppm, and more particularly less than 10 ppm by weight.

[0034] Step i) of the method of the present invention enables the fluorination of chlorine compounds, such as 1,1,3,3-tetrachloropropene (1230za), 1,3,3,3-tetrachloropropene (1230zd), or 1,1,1,3,3-pentachloropropane (240fa). The liquid phase thus accumulates fluorinated organic compounds while maintaining a low HF content.

[0035] The low-HF liquid phase is preferably a liquid phase containing less than 15% by weight of HF, advantageously less than 10% by weight of HF, preferably less than 8% by weight of HF, more preferably less than 6% by weight of HF, particularly less than 5% by weight of HF, even more particularly less than 4% by weight of HF, and preferably less than 2% by weight of HF, based on the total weight of the liquid phase.

[0036] During step i), the liquid phase may contain at least 10% by weight of formula (I)C3H n F m Cl p The compound of formula (I), wherein n is an integer from 0 to 8, m is an integer from 0 to 8, and p is an integer from 0 to 8; preferably, n is an integer from 0 to 8, m is an integer from 0 to 6, and p is an integer from 0 to 6. The compound of formula (I) may be, for example, C3Cl6, C3H4Cl4, or C3H3Cl5.

[0037] Preferably, during step i), the liquid phase may contain at least 10% by weight of formula (I)C3H n F m Cl p The compound of formula (I) wherein n is an integer from 1 to 8, m is an integer from 0 to 4, and p is an integer from 0 to 4; preferably, n is an integer from 1 to 4, m is an integer from 0 to 3, and p is an integer from 2 to 4. The compound of formula (I) may be a propane or propylene compound containing one or more chlorine atoms and / or one or more fluorine atoms. The liquid phase may preferably contain at least 10% by weight of a compound of formula (I) selected from C3H2Cl4, C3H2Cl3F, C3H2Cl2F2, C3H3Cl5, C3H3Cl4F, C3H3Cl3F2, and C3H3Cl2F3. More particularly, the liquid phase may contain at least 10% by weight of a compound of formula (I) selected from C3H2Cl4, C3H2Cl3F, and C3H2Cl2F2.

[0038] The liquid phase may contain at least 15% by weight of formula (I)C3H n F m Cl p(I) compounds, wherein n is an integer from 0 to 8, m is an integer from 0 to 8, and p is an integer from 0 to 8; preferably, n is an integer from 0 to 8, m is an integer from 0 to 6, and p is an integer from 0 to 6.

[0039] More specifically, during step i), the liquid phase may contain at least 15% by weight of formula (I)C3H n F m Cl p The liquid phase comprises a compound of formula (I), wherein n is an integer from 1 to 8, m is an integer from 0 to 4, and p is an integer from 0 to 4; preferably, n is an integer from 1 to 4, m is an integer from 0 to 3, and p is an integer from 2 to 4. The liquid phase preferably comprises at least 15% by weight of a compound of formula (I) selected from C3H2Cl4, C3H2Cl3F, C3H2Cl2F2, C3H3Cl5, C3H3Cl4F, C3H3Cl3F2, and C3H3Cl2F3. More particularly, the liquid phase may comprise at least 15% by weight of a compound of formula (I) selected from C3H2Cl4, C3H2Cl3F, and C3H2Cl2F2.

[0040] The liquid phase may contain at least 20%, at least 30%, at least 40%, at least 50%, at least 60%, at least 70%, at least 80%, or at least 90% by weight of formula (I)C3H n F m Cl p (I) compounds, wherein n is an integer from 0 to 8, m is an integer from 0 to 8, and p is an integer from 0 to 8; preferably, n is an integer from 0 to 8, m is an integer from 0 to 6, and p is an integer from 0 to 6.

[0041] The liquid phase may contain at least 20%, at least 30%, at least 40%, at least 50%, at least 60%, at least 70%, at least 80%, or at least 90% by weight of formula (I)C3H n F m Cl p The compound of formula (I), wherein n is an integer from 1 to 8, m is an integer from 0 to 4, and p is an integer from 0 to 4; preferably, n is an integer from 1 to 4, m is an integer from 0 to 3, and p is an integer from 2 to 4. The liquid phase may preferably comprise at least 20%, at least 30%, at least 40%, at least 50%, at least 60%, at least 70%, at least 80%, or at least 90% by weight of a compound of formula (I) selected from C3H2Cl4, C3H2Cl3F, C3H2Cl2F2, C3H3Cl5, C3H3Cl4F, C3H3Cl3F2, and C3H3Cl2F3.

[0042] More specifically, the liquid phase may contain at least 20%, at least 30%, at least 40%, at least 50%, at least 60%, at least 70%, at least 80%, or at least 90% by weight of a compound of formula (I) selected from C3H2Cl4, C3H2Cl3F, and C3H2Cl2F2.

[0043] The liquid phase may also contain heavy compounds that are dimers or polymers of compounds of formula (I) as defined above.

[0044] Step i) is preferably carried out in the absence of a catalyst.

[0045] Step i) can alternatively be carried out in the presence of a catalyst. The catalyst may be a TiCl4 or SbCl5 catalyst. The catalyst may also be an ionic liquid. Suitable ionic liquids may be Lewis acid derivatives based on aluminum, titanium, niobium, tantalum, tin, antimony, nickel, zinc, or iron. The term "ionic liquid" refers to a non-aqueous salt with ionic properties that is liquid at moderate temperatures (preferably below 120°C). Ionic liquids are preferably obtained from the reaction between an organic salt and an inorganic compound. Ionic liquids are preferably obtained by reacting at least one halogen or oxyhalogen Lewis acid based on aluminum, titanium, niobium, tantalum, tin, antimony, nickel, zinc, or iron with a general formula Y. + A - The salt is obtained by the reaction of A. - This indicates a halide anion (bromine, iodide, and, preferably, chloride or fluoride) or hexafluoroantimonate (SbF6). - And Y + This indicates a quaternary ammonium, quaternary phosphorus, or tertiary sulfonium cation. Halogen Lewis acids based on aluminum, titanium, niobium, tantalum, antimony, nickel, zinc, or iron can be chlorine, bromine, fluorine, or a mixture thereof, such as chlorofluoric acid. More specifically mentioned are chlorides, fluorides, or chlorofluorides having the following formula:

[0046] TiCl x F y Where x + y = 4 and 0 <= x <= 4

[0047] TaCl x F y Where x + y = 5 and 0 <= x <= 5

[0048] NbCl x F y Where x + y = 5 and 0 <= x <= 5

[0049] SnCl x F y Where x + y = 4 and 1 ≤ x ≤ 4

[0050] SbCl x F yWhere x + y = 5 and 0 <= x <= 5

[0051] AlCl x F y Where x + y = 3 and 0 <= x <= 3

[0052] NiCl x F y Where x + y = 2 and 0 <= x <= 2

[0053] FeCl x F y Where x + y = 3 and 0 <= x <= 3

[0054] Examples of such compounds include TiCl4, TiF4, TaCl5, TaF5, NbCl5, NbF5, SbCl5, SbCl4F, SbCl3F2, SbCl2F3, SbClF4, SbF5, and mixtures thereof. The following compounds are preferred: TiCl4, TaCl5+TaF5, NbCl5+NbF5, SbCl5, SbFCl4, SbF2Cl3, SbF3Cl2, SbF4Cl, SbF5, and SbCl5+SbF5. Antimony-based compounds are particularly preferred. Examples of oxyhalides Lewis acids usable according to the invention include TiOCl2, TiOF2, and SbOCl. x F y (x+y=3). In salt Y + A - In the middle, cation Y + It can correspond to one of the following general formulas: R 1 R 2 R 3 R 4 N + R 1 R 2 R 3 R 4 P + R 1 R 2 R 3 S + , where the symbol R 1 To R 4 These are the same or different, each representing a saturated or unsaturated, cyclic or acyclic, or aromatic hydrocarbon group having 1 to 10 carbon atoms, a chloroalkyl group, a fluoroalkyl group, a chlorofluoroalkyl group, or a fluoroalkyl group, wherein one or more of these groups may also contain one or more heteroatoms, such as N, P, S, or O. Ammonium, phosphonium, or sulfonium cations Y +It can also form part of a saturated or unsaturated or aromatic heterocycle having 1 to 3 nitrogen, phosphorus, or sulfur atoms, and can correspond to one or more of the following general formulas:

[0055]

[0056] Where R 1 and R 2 As defined above. Salts containing two or three ammonium, phosphonium, or sulfone sites in their formula are also suitable for use. As salt Y + A - Examples may include tetraalkylammonium chloride and tetraalkylammonium fluoride, tetraalkylphosphonium chloride and tetraalkylphosphonium fluoride, trialkylsulfonium chloride and trialkylsulfonium fluoride, alkylpyridinium chloride and alkylpyridinium fluoride, dialkylimidazolium chloride, dialkylimidazolium fluoride and dialkylimidazolium bromide, and trialkylimidazolium chloride and trialkylimidazolium fluoride. Trimethylsulfonium fluoride or trimethylsulfonium chloride, N-ethylpyridinium chloride or N-ethylpyridinium fluoride, N-butylpyridinium chloride or N-butylpyridinium fluoride, 1-ethyl-3-methylimidazolium chloride or 1-ethyl-3-methylimidazolium fluoride, and 1-butyl-3-methylimidazolium chloride or 1-butyl-3-methylimidazolium fluoride are of particular value. Ionic liquids can be produced in a manner known per se by appropriately mixing halogens or oxyhalogen Lewis acids and organic salts Y. + A - The preparation can be made by referring in particular to the method described in WO 01 / 81353. The catalyst may alternatively be trifluoromethanesulfonic acid or trifluoroacetic acid as described in US 6,166,274.

[0057] According to a preferred embodiment, in addition to 1-chloro-3,3,3-trifluoropropene, stream A also contains a co-product selected from 1,3,3,3-tetrafluoropropene and 1,1,1,3,3-pentafluoropropane. The 1-chloro-3,3,3-trifluoropropene collected in stream A is in the form of a mixture of the two isomers Z and E as described above.

[0058] According to a preferred embodiment, the amount of the co-product selected from 1,3,3,3-tetrafluoropropene and 1,1,1,3,3-pentafluoropropane in stream A is less than 0.5 mol%. The 1,3,3,3-tetrafluoropropene content in stream A is preferably less than 0.5 mol%, more preferably less than 0.4 mol%, and particularly less than 0.3 mol%. The 1,1,1,3,3-pentafluoropropane content in stream A is preferably less than 0.1 mol%, more preferably less than 0.075 mol%, and particularly less than 0.05 mol%.

[0059] The logistics A may also contain HF and HCl.

[0060] Step i) is preferably carried out at a temperature of 50°C to 150°C, and more preferably at a temperature of 75°C to 100°C.

[0061] Step i) is preferably carried out at a pressure of 5 to 20 bara, more preferably at a pressure of 10 to 18 bara, and more particularly at a pressure of 12 to 18 bara.

[0062] The HF / [chlorinated compound] molar ratio at the reactor inlet is preferably between 5 and 10, more preferably between 5 and 7, and even more particularly between 5 and 6. More specifically, when the chlorinated compound in the starting composition is 1,1,3,3-tetrachloropropene (1230za), the HF / 1230za molar ratio is between 5 and 10, more preferably between 5 and 7, and even more particularly between 5 and 6.

[0063] The method preferably further comprises the following steps: (ii) at least one step of: processing stream A to provide stream B containing E-1-chloro-3,3,3-trifluoropropene, HCl, HF and Z-1-chloro-3,3,3-trifluoropropene, and stream C mainly containing HF (e.g., at least 50% by weight, preferably at least 70% by weight of HF); (iii) at least one step of: collecting hydrochloric acid from stream B to provide stream D containing HCl and stream E containing E-1-chloro-3,3,3-trifluoropropene, HCl, HF and Z-1-chloro-3,3,3-trifluoropropene; (iv) at least one step of: purifying stream E obtained from step (iii) to provide E-1233zd, preferably having a purity of not less than 98%, advantageously not less than 99%, and very advantageously not less than 99.9% by weight.

[0064] Prior to the purification step, the stream E obtained in step (iii) preferably undergoes at least one separation step to provide a stream primarily containing HF (e.g., at least 90 wt%, preferably at least 98 wt%, and advantageously at least 99 wt%), which can be recycled to the reactor, and a stream containing E-1-chloro-3,3,3-trifluoropropene, HCl, HF, and Z-1-chloro-3,3,3-trifluoropropene. The separation step is preferably decantation, advantageously carried out at a temperature between -50 and 50°C, preferably between -20°C and 10°C.

[0065] Processing step (ii) is preferably carried out in a reflux tower, advantageously at a temperature between 30 and 120°C, to provide the feed stream C to be recycled back to the reactor.

[0066] In step (iii), HCl is preferably collected via a distillation column equipped with a bottom reboiler and a top reflux system. The bottom temperature is advantageously between 20 and 110°C. The top temperature is advantageously between -50 and 0°C. HCl distillation is typically carried out at pressures between 7 and 25 bar.

[0067] According to one embodiment, the purification step (iv) preferably includes at least one distillation step, and advantageously at least two distillation steps. According to a preferred embodiment, the purification step (iv) includes at least one washing step with water and / or washing with an alkaline solution, a drying step, and at least one distillation step. The purpose of this distillation step is to remove both light and heavy products, which can be partially recycled back to the reactor, depending on whether they are recyclable.

[0068] The method is preferably performed continuously.

[0069] According to a second aspect, the present invention provides a composition comprising at least 98 mol% of (E / Z)-1-chloro-3,3,3-trifluoropropene and less than 0.5 mol% of a co-product selected from 1,3,3,3-tetrafluoropropene and 1,1,1,3,3-pentafluoropropane. The composition preferably comprises at least 99 mol% of (E / Z)-1-chloro-3,3,3-trifluoropropene and less than 0.5 mol% of a co-product selected from 1,3,3,3-tetrafluoropropene and 1,1,1,3,3-pentafluoropropane. More particularly, the composition comprises at least 99.5 mol% of (E / Z)-1-chloro-3,3,3-trifluoropropene and less than 0.5 mol% of a co-product selected from 1,3,3,3-tetrafluoropropene and 1,1,1,3,3-pentafluoropropane.

[0070] The composition preferably comprises at least 99 mol% of (E / Z)-1-chloro-3,3,3-trifluoropropene, less than 0.5 mol% of 1,3,3,3-tetrafluoropropene, and less than 0.1 mol% of 1,1,1,3,3-pentafluoropropane. More particularly, the composition comprises at least 99 mol% of (E / Z)-1-chloro-3,3,3-trifluoropropene, less than 0.4 mol% of 1,3,3,3-tetrafluoropropene, and less than 0.075 mol% of 1,1,1,3,3-pentafluoropropane. Very particularly, the composition comprises at least 99 mol% of (E / Z)-1-chloro-3,3,3-trifluoropropene, less than 0.3 mol% of 1,3,3,3-tetrafluoropropene, and less than 0.05 mol% of 1,1,1,3,3-pentafluoropropane.

[0071] The composition preferably contains at least 99.5 mol% of (E / Z)-1-chloro-3,3,3-trifluoropropene, less than 0.3 mol% of 1,3,3,3-tetrafluoropropene, and less than 0.05 mol% of 1,1,1,3,3-pentafluoropropane.

[0072] According to a preferred embodiment, the composition is obtained at the outlet of a reactor carrying out the method according to the invention.

[0073] This invention includes the following aspects / implementations / features in any order and / or in any combination:

[0074] 1. A method for producing 1-chloro-3,3,3-trifluoropropene, comprising step i) contacting hydrofluoric acid (HF) with a starting composition in a reactor to produce a stream A comprising 1-chloro-3,3,3-trifluoropropene (1233zd), said starting composition comprising at least one chlorine compound selected from 1,1,3,3-tetrachloropropene (1230za), 1,3,3,3-tetrachloropropene (1230zd) and 1,1,1,3,3-pentachloropropane (240fa) or mixtures thereof, characterized in that step i) is carried out in a low-HF liquid phase.

[0075] 2. The method of any of the foregoing or subsequent embodiments / features / aspects, characterized in that the low-HF liquid phase is a liquid phase containing less than 15% by weight of HF, advantageously less than 10% by weight of HF, preferably less than 8% by weight of HF, more preferably less than 6% by weight of HF, particularly less than 5% by weight of HF, even more particularly less than 4% by weight of HF, preferably less than 2% by weight of HF, based on the total weight of the liquid phase.

[0076] 3. The method of any of the foregoing or subsequent embodiments / features / aspects, characterized in that the at least one chlorine compound is 1,1,3,3-tetrachloropropene (1230za).

[0077] 4. The method of any of the foregoing or subsequent embodiments / features / aspects, characterized in that the starting composition comprises at least 10% by weight of the at least one chlorine compound, based on the total weight of the starting composition.

[0078] 5. The method of any of the foregoing or subsequent embodiments / features / aspects, characterized in that the starting composition contains less than 10% by weight of HF, based on the total weight of the starting composition.

[0079] 6. The method of any of the foregoing or subsequent embodiments / features / aspects, characterized in that the liquid phase comprises at least 10% by weight of formula (I)C3H n F m Cl p (I) compounds, where n is an integer from 0 to 8, m is an integer from 0 to 8, and p is an integer from 0 to 8.

[0080] 7. The method of any of the foregoing or subsequent embodiments / features / aspects, characterized in that step i) is carried out in the absence of a catalyst.

[0081] 8. The method of any of the foregoing or subsequent embodiments / features / aspects, characterized in that stream A comprises a common product selected from 1,3,3,3-tetrafluoropropene and 1,1,1,3,3-pentafluoropropane.

[0082] 9. The method of any of the foregoing or subsequent embodiments / features / aspects, characterized in that the amount of the co-product selected from 1,3,3,3-tetrafluoropropene and 1,1,1,3,3-pentafluoropropane is less than 0.5% by weight, based on the total weight of stream A at the reactor outlet.

[0083] 10. The method of any of the foregoing or subsequent embodiments / features / aspects, characterized in that step i) is carried out at a temperature of 50°C to 150°C.

[0084] 11. The method of any of the foregoing or subsequent embodiments / features / aspects, characterized in that step i) is performed under a pressure of 5 to 20 bara.

[0085] 12. A composition comprising at least 98 mol% of (E / Z)-1-chloro-3,3,3-trifluoropropene and less than 0.5 mol% of a co-product selected from 1,3,3,3-tetrafluoropropene and 1,1,1,3,3-pentafluoropropane.

[0086] 13. The composition of any of the foregoing or subsequent embodiments / features / aspects, comprising at least 99.5 mol% of (E / Z)-1-chloro-3,3,3-trifluoropropene, less than 0.3 mol% of 1,3,3,3-tetrafluoropropene and less than 0.05 mol% of 1,1,1,3,3-pentafluoropropane.

[0087] 14. The composition of any of the foregoing or subsequent embodiments / features / aspects, characterized in that it is obtained at the outlet of the reactor carrying out the method as described in any one of claims 1 to 11.

[0088] Example

[0089] The equipment used consists of a 60-liter reactor made of 316L stainless steel. It has devices for measuring temperature, pressure, and liquid level. Reactants are fed through an immersion tube, while the resulting products are circulated through a 5-meter reflux column before condensation at the top. This column is filled with structured metallic packing, which allows for the separation of low-boiling products, while the feed, intermediate compounds, and unreacted HF fall back into the reactor. Pressure regulators apply operating pressure to the components. An in-line recovery system allows for sampling of the effluent gas stream, which is directed to a gas chromatograph. Reactants are fed continuously, and products are analyzed and collected continuously.

[0090] Example 1 (Comparative)

[0091] 25 liters of HF were introduced into the reactor. The reactor was maintained at a temperature of 90°C. The pressure was adjusted to 15 bara. The reactants were then fed at the following rates: 2 kg / h of HF and 3.5 kg / h of 1230 zirconium, which provided a molar ratio of 5.2 of HF to organic compounds. The composition of the resulting gas stream after five hours of operation is provided in Table 1.

[0092] Example 2

[0093] The procedure of Example 1 was repeated with an initial volume of 25 liters of a mixture containing organic compounds but free of HF. The mixture contained, by weight, 10.7% 1230za, 0.9% 1231 (trichloromonofluoropropylene) isomer, and 5.7% 1232 (dichlorodifluoropropylene) isomer. The balance consisted primarily of dimers and heavy compounds. The reactor was heated in the same manner as before, and the reactants were then fed at a rate of 2 kg / h of HF and 3.3 kg / h of 1230za, providing a molar ratio of 5.4 of HF to organic compounds. The composition of the resulting gas stream after 5 hours of operation is provided in Table 1.

[0094] Example 3

[0095] The procedure of Example 1 was repeated with a starting volume of 25 liters of 1230za alone. The reactor was heated in the same manner as before, and then the reactants were fed at the following rates: 1.8 kg / h of HF and 2.9 kg / h of 1230za, which provided a molar ratio of 5.6 for HF to 1230za. The composition of the resulting gas stream after 5 hours of operation is provided in Table 1.

[0096] Table 1

[0097]

Claims

1. A composition in a reactor comprising a starting composition comprising at least one chlorine compound selected from 1,1,3,3-tetrachloropropene (1230za), 1,3,3,3-tetrachloropropene (1230zd), and 1,1,1,3,3-pentachloropropane (240fa), or mixtures thereof, and HF, wherein the composition in the reactor is a low-HF liquid phase comprising less than 15% by weight of HF, based on the total weight of the composition in the reactor.

2. The composition as claimed in the preceding claims, characterized in that it is carried out in a reactor for a method of producing 1-chloro-3,3,3-trifluoropropene, the method comprising step i) contacting hydrofluoric acid (HF) with a starting composition in the reactor to produce stream A comprising 1-chloro-3,3,3-trifluoropropene (1233zd), said starting composition comprising at least one chlorine compound selected from 1,1,3,3-tetrachloropropene (1230za), 1,3,3,3-tetrachloropropene (1230zd) and 1,1,1,3,3-pentachloropropane (240fa) or mixtures thereof, characterized in that step i) is carried out in a low HF liquid phase.

3. The composition of claim 2, characterized in that the low-HF liquid phase is a liquid phase containing less than 10% by weight of HF, based on the total weight of the composition in the reactor.

4. The composition of claim 3, characterized in that the low-HF liquid phase is a liquid phase containing less than 8% by weight of HF, based on the total weight of the composition in the reactor.

5. The composition of claim 3, characterized in that the low-HF liquid phase is a liquid phase containing less than 6% by weight of HF, based on the total weight of the composition in the reactor.

6. The composition of claim 3, characterized in that the low-HF liquid phase is a liquid phase containing less than 5% by weight of HF, based on the total weight of the composition in the reactor.

7. The composition of claim 3, characterized in that the low-HF liquid phase is a liquid phase containing less than 4% by weight of HF, based on the total weight of the composition in the reactor.

8. The composition of claim 3, characterized in that the low-HF liquid phase is a liquid phase containing less than 2% by weight of HF, based on the total weight of the composition in the reactor.

9. The composition according to any one of claims 2-8, characterized in that the at least one chlorine compound is 1,1,3,3-tetrachloropropene (1230za).

10. The composition according to any one of claims 2-8, characterized in that the starting composition comprises at least 10% by weight of the at least one chlorine compound, based on the total weight of the starting composition.

11. The composition of any one of claims 2-8, characterized in that the starting composition contains less than 10% by weight of HF, based on the total weight of the starting composition.

12. The composition according to any one of claims 2-8, characterized in that the liquid phase comprises at least 10% by weight of formula (I)C3H n F m Cl p (I) compounds, where n is an integer from 0 to 8, m is an integer from 0 to 8, and p is an integer from 0 to 8.

13. The composition according to any one of claims 2-8, characterized in that step i) is carried out in the absence of a catalyst.

14. The composition according to any one of claims 2-8, characterized in that stream A comprises a co-product selected from 1,3,3,3-tetrafluoropropene and 1,1,1,3,3-pentafluoropropane.

15. The composition of claim 9, characterized in that the amount of the co-product selected from 1,3,3,3-tetrafluoropropylene and 1,1,1,3,3-pentafluoropropane is less than 0.5% by weight, based on the total weight of stream A at the reactor outlet.

16. The composition according to any one of claims 2-8, characterized in that step i) is carried out at a temperature of 50°C to 150°C.

17. The composition according to any one of claims 2-8, characterized in that step i) is carried out at a pressure of 5 to 20 bara.

Images