Integrated process for making 1-chloro-3,3,3-trifluoropropene (HCFO-1233zd) from a mixture of high boiling fluorinated components

Abstract

The present disclosure provides a process for converting a mixture of high-boiling fluorinated components including 1,1,3,3-tetrachloro-1-fluoropropane (HCFC-241fa), 1,3,3-trichloro-1,1-difluoropropane (HCFC-242fa), 1,1,3-trichloro-1,3-difluoropropane (HCFC-242fb), 3,3-dichloro-1,1,1-trifluoropropane (HCFC-243fa), 1,3-dichloro-1,1,3-trifluoropropane (HCFC-243fb), 3-chloro-1,1,1,3-tetrafluoropropane (HCFC-244fa), isomers thereof, and combinations thereof, to 1-chloro-3,3,3-trifluoropropene (HCFO-1233zd). Heavy impurities such as oligomers and other high boiling impurities present may be purged during the process to prevent yield losses and reduced catalyst efficiency.

Description

[Technical field]

[0001] (CROSS REFERENCE TO RELATED APPLICATIONS) This application is an international application of U.S. Patent Application No. 18 / 083,238, filed December 16, 2022, and claims priority to U.S. Provisional Patent Application No. 63 / 331,966, filed April 18, 2022, and International Application No. CN / 2022 / 073904, filed January 26, 2022, all of which are incorporated by reference in their entireties herein.

[0002] FIELD OF THEINVENTION The present disclosure relates to an integrated process for making E-1-chloro-3,3,3-trifluoropropene (HCFO-1233zd(E)) and Z-1-chloro-3,3,3-trifluoropropene (HCFO-1233zd(Z)) from a mixture of high-boiling fluorinated components. [Background technology]

[0003] Chlorofluorocarbons (CFCs), such as trichlorofluoromethane and dichlorodifluoromethane, have been used as refrigerants, blowing agents, and diluents for gas sterilization. In recent years, there has been widespread concern that certain chlorofluorocarbons may be harmful to the Earth's ozone layer. Therefore, there has been a global effort to use halocarbons that contain fewer or no chlorine substituents. Thus, the production of hydrofluorocarbons, or compounds that contain only carbon, hydrogen, and fluorine, has become of increasing interest to provide environmentally desirable products for use as solvents, blowing agents, refrigerants, cleaning agents, aerosol propellants, heat transfer media, dielectrics, fire extinguishing compositions, and power cycle working fluids.

[0004] In this regard, E-1-chloro-3,3,3-trifluoropropene (HCFO-1233zd(E)) is a compound that has the potential to be used as a zero Ozone Depletion Potential (ODP) and low Global Warming Potential (GWP) refrigerant, blowing agent, aerosol propellant, solvent, etc., as well as a fluorinated monomer. Summary of the Invention

[0005] The present disclosure provides a process for converting a mixture of high-boiling fluorinated components to 1-chloro-3,3,3-trifluoropropene (HCFO-1233zd). The mixture of high-boiling fluorinated components may include 1,1,3,3-tetrachloro-1-fluoropropane (HCFC-241fa), 1,3,3-trichloro-1,1-difluoropropane (HCFC-242fa), 1,1,3-trichloro-1,3-difluoropropane (HCFC-242fb), 3,3-dichloro-1,1,1-trifluoropropane (HCFC-243fa), 1,3-dichloro-1,1,3-trifluoropropane (HCFC-243fb), 3-chloro-1,1,1,3-tetrafluoropropane (HCFC-244fa), isomers thereof, and combinations thereof. Heavy impurities such as oligomers and other high boiling impurities such as hexachloroethane that are present may be purged during the process to prevent yield losses and reduced catalyst efficiency. [Brief description of the drawings]

[0006] The above-mentioned and other features of the present disclosure, as well as the manner in which they are achieved, will become more apparent, and the disclosure itself will be better understood, by referring to the following description of the embodiments of the present disclosure in light of the accompanying drawings, in which: [Figure 1] FIG. 1 shows a schematic diagram of a process for the synthesis of 1-chloro-3,3,3-trifluoropropene (HCFO-1233zd) from a mixture of high-boiling fluorinated components.

[0007] Corresponding reference characters indicate corresponding parts throughout the several views. Although the drawings depict embodiments of various features and components in accordance with the present disclosure, the drawings are not necessarily to scale and certain features may be exaggerated to better illustrate and explain the present disclosure. The exemplifications set forth herein are illustrative of embodiments of the present disclosure, and such exemplifications should not be construed as limiting the scope of the present disclosure in any manner. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0008] The present disclosure provides a process for making 1-chloro-3,3,3-trifluoropropene (HCFO-1233zd) from a mixture of high-boiling fluorinated components. Specifically, the present disclosure provides a method for producing 1-chloro-3,3,3-trifluoropropene (HCFO-1233zd) from high-boiling fluorinated components produced as by-products from a process for producing 1-chloro-3,3,3-trifluoropropene (HCFO-1233zd) from 1,1,1,3,3-pentachloropropene (HCC-240fa). The combined by-product stream may be co-converted to 1-chloro-3,3,3-trifluoropropene (HCFO-1233zd).

[0009] 1-Chloro-3,3,3-trifluoropropene (HCFO-1233zd) can be produced industrially by the reaction shown in Equation 1 below. Formula 1: HCC-240fa+3HF→HCFO-1233zd+4HCl

[0010] In this process, 1-chloro-3,3,3-trifluoropropene (HCFO-1233zd) can be produced in a liquid phase reaction without the need for a catalyst. Briefly, anhydrous hydrogen fluoride (HF) can be mixed with 1,1,1,3,3-pentachloropropene (HCC-240fa) at high temperature and pressure to produce the desired 1-chloro-3,3,3-trifluoropropene (HCFO-1233zd) as a mixture of E and Z isomers.

[0011] During the course of the reaction, partially fluorinated by-products such as 1,1,3,3-tetrachloro-1-fluoropropane (HCFC-241fa), 1,3,3-trichloro-1,1-difluoropropane (HCFC-242fa), 3,3-dichloro-1,1,1-trifluoropropane (HCFC-243fa), and 3-chloro-1,1,1,3-tetrafluoropropane (HCFC-244fa), along with their other isomers, may be produced according to Equations 2-5 shown below. Formula 2: HCC-240fa+HF→HCFC-241 isomer+HCl Formula 3: HCC-240fa+2HF→HCFC-242 isomer+2HCl Formula 4: HCC-240fa+3HF→HCFC-243 isomer+3HCl Formula 5: HCC-240fa+4HF→HCFC-244 isomer+4HCl

[0012] A mixture of high boiling fluorinated components may be defined as a mixture of fluorinated components having a boiling point higher than 39° C., in other words higher than the boiling point of Z-1-chloro-3,3,3-trifluoropropene (HCFO-1233zd(Z)). High boiling fluorinated components may include compounds that can be converted to 1-chloro-3,3,3-trifluoropropene (HCFO-1233zd) using the methods described herein. Suitable such components may include 1,1,3,3-tetrachloro-1-fluoropropane (HCFC-241fa), 1,3,3-trichloro-1,1-difluoropropane (HCFC-242fa), 3,3-dichloro-1,1,1-trifluoropropane (HCFC-243fa), and 3-chloro-1,1,1,3-tetrafluoropropane (HCFC-244fa), along with their other isomers. For example, another isomer of HCFC-242 is 1,1,3-trichloro-1,3-difluoropropane (HCFC-242fb), and another isomer of HCFC-243 is 1,3-dichloro-1,1,3-trifluoropropane (HCFC-243fb).

[0013] Other by-products that may be present in the feed stream or reactor stream include oligomers. As used herein, oligomers can be defined as dimers, trimers, tetramers, and other groups of repeating and / or mixed monomer units that cannot be readily converted to 1-chloro-3,3,3-trifluoropropene (HCFO-1233zd) using the methods described herein.

[0014] Other impurities that may also be present in the reactor as by-products include very high boiling impurities, i.e. impurities with a boiling point higher than about 140° C. These very high boiling impurities may include CC-110 (hexachloroethane), HCO-1230 (tetrachloropropene) isomers, and some oligomers. An example of an HCO-1230 isomer may be HCO-1230za (1,1,3,3-tetrachloropropene). A possible example of an oligomer may be the dimer of 1,3,3-trichloro-3-fluoropropene (HCFO-1231zd) and 1,3-dichloro-3,3-difluoropropene (HCFO-1232zd), which has the chemical formula CHFCl. For the purposes of this invention, these very high boiling impurities, including CC-110, HCO-1230, and oligomers, may also be referred to as heavy impurities.

[0015] The present disclosure provides a process for maximizing the production of 1-chloro-3,3,3-trifluoropropene (HCFO-1233zd) by reacting a mixture of high-boiling fluorinated components with HF in the presence of a catalyst to produce 1-chloro-3,3,3-trifluoropropene (HCFO-1233zd) and removing undesirable heavy impurities.

[0016] Briefly, the reactor product from equation 1 is first separated, excess HF is recovered and recycled, and hydrogen chloride (HCl) is removed and recovered. The remaining mixture contains the E and Z isomers of 1-chloro-3,3,3-trifluoropropene (HCFO-1233zd), high-boiling fluorinated components, low-boiling impurities, particularly the E and Z isomers of 1,1,1,3,3-pentafluoropropane (HFC-245fa), trifluoropropyne, and 1,3,3,3-tetrafluoropropene (HFO-1234ze), and a small amount (usually 2% by weight or less) of residual HF. This mixture can be subjected to distillation to remove the high-boiling fluorinated components from 1-chloro-3,3,3-trifluoropropene (HCFO-1233zd), low-boiling impurities, and HF.

[0017] After distillation, the high boiling fluorinated components in the vapor phase may be passed together with HF to another reactor. The reactor may contain a catalyst. Without being bound by theory, it is possible that the presence of heavy impurities in the reactor may reduce the catalyst activity. Therefore, the unwanted heavy impurities may be purged before entering the reactor. After the reaction, any heavy impurities produced may be purged before purification of the desired product.

[0018] An example of the process is shown in Figure 1 and summarized below. As shown, a stream 12 of high boiling fluorinated components and heavy impurities recovered from the reaction of 1,1,1,3,3-pentachloropropene (HCC-240fa) stored in a high boiler tank 10 with anhydrous HF (not shown) may be combined with a stream 16 containing HF from a HF feed source 14. The combined stream 18 may be passed to a vaporizer 20. After vaporization, the heavy impurities 22 may be passed to a heavy impurities storage tank 24 for later disposal, while a stream 26 containing high boiling fluorinated components and HF may be passed to a reactor 30. A heating system 36 may be used to cool 32 or heat 34 the reactor 30. The reactor 30 is a gas phase reactor in which the contents of stream 26 react in the gas phase according to the conditions described below. From the reactor 30, a crude product stream 38 containing the E and Z isomers of 1-chloro-3,3,3-trifluoropropene (HCFO-1233zd), HF, HCl, and newly formed heavy impurities may be passed to a partial condenser 40. At least a portion of the heavy impurities 42 may be removed from the partial condenser 40 and passed to a heavy impurities storage tank 24. A product stream 44 containing the E and Z isomers of 1-chloro-3,3,3-trifluoropropene (HCFO-1233zd) may be combined with a second stream 46 containing the E and Z isomers of 1-chloro-3,3,3-trifluoropropene (HCFO-1233zd) from the reaction of 1,1,1,3,3-pentachloropropene (HCC-240fa) with HF (not shown) and passed as combined stream 48 to a distillation column 50. A bottom product 52 may be recycled back to the high boiler tank 10.The overhead stream 54, containing primarily E-1-chloro-3,3,3-trifluoropropene (HCFO-1233zd(E)), can be sent to a purification column (not shown in FIG. 1 ) to isolate and recover purified E-1-chloro-3,3,3-trifluoropropene (HCFO-1233zd(E)) product and recyclable by-products including Z-1-chloro-3,3,3-trifluoropropene (HCFO-1233zd(Z)) and 3-chloro-1,1,1,3-tetrafluoropropane (HCFC-244fa), which can be further converted to E-1-chloro-3,3,3-trifluoropropene (HCFO-1233zd(E)).

[0019] The hydrogen fluoride (HF) feed may be anhydrous. In other words, the hydrogen fluoride (HF) feed may be substantially free of water. The amount of water present in the hydrogen fluoride (HF) feed may be about 1000 ppm or less, about 750 ppm or less, about 500 ppm or less, about 250 ppm or less, about 100 ppm or less, about 50 ppm or less, about 25 ppm or less, about 10 ppm or less, about 5 ppm or less, or about 1 ppm or less.

[0020] The temperature at the outlet of the vaporizer / superheater 20 may be controlled to be about 200° C. or greater, about 220° C. or greater, about 250° C. or greater, about 300° C. or greater, about 350° C. or greater, or about 400° C. or greater, or within any range between these endpoints.

[0021] The reaction in reactor 30 can be carried out in any suitable reaction vessel or reactor, but should preferably be constructed from materials that are resistant to the corrosive effects of hydrogen fluoride, such as nickel and its alloys, including Hastelloy, Inconel, Incoloy, and Monel. These may be single pipes or multiple tubes packed with a solid catalyst. Suitable reactors may include, for example, catalytic pipe reactors.

[0022] The temperature in reactor 30 can be about 200° C. or more, about 210° C. or more, about 220° C. or more, about 230° C. or more, about 240° C. or more, about 250° C. or less, about 260° C. or less, about 270° C. or less, about 280° C. or less, about 290° C. or less, about 300° C. or less, about 310° C. or less, about 325° C. or less, about 350° C. or less, about 400° C. or less, or any value or range encompassed by these endpoints.

[0023] The pressure in reactor 30 can be maintained at about 2 psig or more, about 5 psig or more, about 10 psig or more, about 15 psig or more, about 20 psig or more, about 25 psig or less, about 30 psig or less, about 35 psig or less, about 40 psig or less, about 45 psig or less, about 50 psig or less, about 75 psig or less, about 100 psig or less, or any value or range encompassed by these endpoints.

[0024] The molar ratio of HF / (HCFC-241 isomers+HCFC-242 isomers) can be about 0.5 / 1 or more, about 0.7 / 1 or more, about 0.9 / 1 or more, about 1.0 / 1 or more, about 1.1 / 1 or more, about 1.3 / 1 or more, about 1.5 / 1 or more, about 2.0 / 1 or less, about 2.5 / 1 or less, about 3.0 / 1 or less, about 3.5 / 1 or less, about 4.0 / 1 or less, about 5.0 / 1 or less, or any value or range encompassed by these endpoints.

[0025] Suitable catalysts may include chromium oxide, chromium oxyfluoride, and chromium halides. Chromium oxide may include amorphous chromium oxide (Cr2O3), crystalline chromium oxide, and combinations thereof. Chromium oxyfluoride may include fresh amorphous chromium oxide (Cr2O3) pretreated with HF, fresh crystalline chromium oxide (Cr2O3) pretreated with HF, amorphous chromium oxyfluoride (CrO x F y (wherein x may be greater than 0 but less than 1.5, and y may be greater than 0 but less than 3), crystalline chromium oxyfluoride (CrO x F y(wherein x may be greater than 0 but less than 1.5, and y may be greater than 0 but less than 3), and combinations thereof. In one embodiment, the catalyst may include amorphous chromium oxyfluoride (CrO x F y where x can be greater than 0 but less than 1.5, and y can be greater than 0 but less than 3. Chromium halides can include chromium trifluoride (CrF3), chromium trichloride (CrCl3), chromium triiodide (CrI3), and chromium tribromide (CrBr3), and combinations thereof. In one embodiment, the catalyst is chromium trifluoride (CrF3).

[0026] Other suitable catalysts include chromium-based promoted catalysts, which are based on chromium and contain an amount of at least one cocatalyst selected from Ni, Zn, Co, Mn, Mg, or mixtures thereof. The amount of cocatalyst may be 0.1% to 20% by weight based on the total weight of the catalyst, and more specifically may be present in an amount as small as 0.1%, 0.5%, 1.0%, 1.5% or as large as 2.0%, 3.0%, 4.0%, 5.0%, 6.0% by weight based on the total weight of the catalyst, or in any range using any two of these values ​​as endpoints. One suitable chromium promoted catalyst is a zinc / chromia catalyst based on chromia and containing an amount of zinc as a cocatalyst, such as the JM 62-3M catalyst available from Johnson Matthey. Prior to use, the catalyst may be fluorinated using anhydrous HF under conditions effective to convert some metal oxides to the corresponding metal fluorides.

[0027] The chromium-based catalyst may also be a low chromium (VI) catalyst having a total chromium (VI) oxide content of about 5000 ppm or less, about 2000 ppm or less, about 1,000 ppm or less, about 500 ppm or less, about 250 ppm or less, or about 100 ppm or less based on the total chromium oxide in the chromium oxide catalyst.

[0028] In addition to chromium-based catalysts, other suitable catalysts include alumina, iron oxide, magnesium oxide, zinc oxide, nickel oxide, cobalt oxide, aluminum fluoride or metal fluorides such as iron fluoride, magnesium fluoride, zinc fluoride, nickel fluoride, cobalt fluoride, fluorinated alumina, fluorinated iron oxide, fluorinated magnesium oxide, fluorinated nickel oxide, fluorinated cobalt oxide, titanium fluoride, molybdenum fluoride, aluminum oxyfluoride, and combinations thereof. Prior to use, the catalyst containing the metal oxide(s) is subjected to a fluorination treatment using anhydrous HF under conditions effective to convert some of the metal oxides to the corresponding metal fluorides.

[0029] The heating system may include any suitable heating medium capable of achieving and / or maintaining the temperature required for the process. Suitable heating media may include, for example, molten salts, hot oil, high pressure steam, and electric heaters (resistance or induction), among others.

[0030] The partial condenser 40 may be operated at a temperature of about 10° C. or more, about 20° C. or more, about 30° C. or more, about 40° C. or more, about 50° C. or less, about 60° C. or less, about 70° C. or less, about 80° C. or less, or any value or range encompassed by these endpoints.

[0031] The partial condenser 40 may be operated at a pressure of about 1 bar or more, about 2 bar or more, about 3 bar or less, about 4 bar or less, about 5 bar or less, or any value or range encompassed by these endpoints.

[0032] Distillation column 50 may be operated at an overhead temperature of about 10° C. or more, about 20° C. or more, about 30° C. or more, about 40° C. or less, about 50° C. or less, about 60° C. or less, or any value or range encompassed by these endpoints.

[0033] Distillation column 50 may be operated at a pressure of about 1 bar or more, about 2 bar or more, about 3 bar or less, about 4 bar or less, about 5 bar or less, or any value or range encompassed by these endpoints.

[0034] The heavy impurities in the storage tank may be purged or processed, for example, by distillation (such as distillation under vacuum) to produce 1,1,3,3-tetrachloro-1-fluoropropane (HCFC-241fa), 1,3,3-trichloro-1,1-difluoropropane (HCFC-242fa), 1,1,3-trichloro-1,3-difluoropropane (HCFC-242fb), 3,3-dichloro-1,1,1-trifluoropropane (HCFC-243fa), 1,3-dichloro-1,1,3-trifluoropropane (HCFC-243fb), and 3-chloro-1,1,1-trifluoropropane (HCFC-243fb). Valuable components such as 1,1,1,3-tetrafluoropropane (HCFC-244fa) and its isomers (which can be sent to a reactor for conversion to 1-chloro-3,3,3-trifluoropropene (HCFO-1233zd) product, for example), and other valuable components such as 1,1,3,3-tetrachloropropene (HCO-1230za) and its isomers (which can be sent to a 240fa reactor for conversion to 1-chloro-3,3,3-trifluoropropene (HCFO-1233zd) product) can be recovered.

[0035] Light products produced during the process may include E-1,3,3,3-tetrafluoropropene (HFO-1234ze(E)), Z-1,3,3,3-tetrafluoropropene (HFO-1234ze(Z)), and 1,1,3,3-pentafluoropropane (HFC-245fa). Other products produced during the process may include 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf), HCFO-1232, HCFO-1231, and HFO-1230 isomers, 1-chloro-1,3,3,3-tetrafluoropropane (HCFC-244fa), trichloropropene isomers, hexachloroethane, dimers such as CHF isomers, CHF isomers, CHFCl isomers, CHFCl isomers, and CHFCl isomers, among others.

[0036] The conversion of 1,1,3,3-tetrachloro-1-fluoropropane (HCFC-241fa) to 1-chloro-3,3,3-trifluoropropene (HCFO-1233zd) can be about 70% or more, about 80% or more, about 90% or more, about 91% or more, about 92% or more, about 93% or more, about 95% or more, about 96% or more, about 97% or more, about 98% or more, or about 99% or more.

[0037] The conversion of HCFC-242 isomers (non-limiting examples include 1,3,3-trichloro-1,1-difluoropropane (HCFC-242fa) and 1,1,3-trichloro-1,3-difluoropropane (HCFC-242fb)) to 1-chloro-3,3,3-trifluoropropene (HCFO-1233zd) can be about 50% or more, about 60% or more, about 70% or more, about 80% or more, about 90% or more, about 91% or more, about 92% or more, about 93% or more, about 95% or more, about 96% or more, about 97% or more, about 98% or more, about 99% or more, or about 99.5% or more.

[0038] The conversion of HCFC-243 isomers (non-limiting examples include 3,3-dichloro-1,1,1-trifluoropropane (HCFC-243fa) and 1,3-dichloro-1,1,3-trifluoropropane (HCFC-243fb)) to 1-chloro-3,3,3-trifluoropropene (HCFO-1233zd) can be about 20% or more, about 30% or more, about 40% or more, about 45% or more, about 50% or more, about 55% or more, about 60% or more, about 70% or more, about 80% or more, or about 90% or more.

[0039] The conversion of 3-chloro-1,1,1-3-tetrafluoropropane (HCFC-244fa) to 1-chloro-3,3,3-trifluoropropene (HCFO-1233zd) can be about 20% or more, about 30% or more, about 40% or more, about 50% or more, about 60% or more, about 70% or more, about 80% or more, or about 90% or more.

[0040] The overall selectivity for E and Z isomers of 1-chloro-3,3,3-trifluoropropene (HCFO-1233zd) can be about 70% or more, about 75% or more, about 80% or more, about 85% or more, about 90% or more, about 95% or more, or about 99% or more. E-1-chloro-3,3,3-trifluoropropene (HCFO-1233zd(E)) can be separated and purified as product, while Z-1-chloro-3,3,3-trifluoropropene (HCFO-1233zd(Z)) can be separated / recovered and fed to an isomerization reactor and converted to E-1-chloro-3,3,3-trifluoropropene (HCFO-1233zd(E)). EXAMPLES

[0041] Example 1 Conversion of fluorinated compounds to 1233 zd HCFO-1233zd(E)(68.75%), HCFO-1233zd(Z)(4.08%), HCl(0.05%), HF(1.66%), HCFC-241 isomer(5.40%), H CFC-242 isomer (15.98%), HCFC-243 isomer (1.60%), HCFC-244 isomer (0.68%), HFC-245 isomer (0.12%), HCFO-1232zd( The stream containing HCFO-1233zd(E) (0.03%), HFO-1234ze(Z) (1.26%), HFO-1234ze(E) (0.19%), CC-110 (0.02%) and oligomers (0.19%) is subjected to separation by distillation and phase separation of the immiscible liquids to remove HCl, HF and other under-fluorinated intermediates such as HCC-240fa and HCFC-241fa, which are recycled to the reactor. The remaining mixture containing the above components is distilled to remove higher boiling products as a bottoms stream. HCFO-1233zd(E) and HCFO-1233zd(Z) are recovered in the overhead from this distillation to obtain a crude product stream. The crude product stream is then subjected to further purification including caustic scrubbing, water removal, distillation and conversion of HCFO-1233zd(Z) to HCFO-1233zd(E). These purification steps result in HCFO-1233zd(E) of the desired purity.

[0042] The bottoms stream containing the high boiling products is collected in a vessel such as a high boiler tank and then fed by gravity to a vaporizer and superheater along with anhydrous HF to produce a vapor stream containing HF (10.26%), HCFC-241 isomers (19.8%), HCFC-242 isomers (60.37%), HCFC-243 isomers (8.02%), HCFC-244 isomers (0.004%), HCFO-1232zd (0.28%), HCFO-1233zd(Z) (0.018%), and 1.248% heavy impurities. In this example, the vapor stream is heated to 220° C.

[0043] A liquid purge containing HF (0.15%), HCFC-241 isomers (27.98%), HCFC-242 isomers (33.39%), HCFC-243 isomers (1.84%), HCFO-1232zd (0.06%) and heavy impurities (36.58%) is removed from the vaporizer to remove heavy impurities that may adversely affect the catalyst. The vapor stream then enters the reactor where additional HCFO-1233zd is produced by reaction of the high boiling fluorinated compounds with HF. The reactor product stream containing HCFO-1233zd(E) (51.23%), HCFO-1233zd(Z) (0.4%), HCl (32.75%), HF (0.91%), HCFC-241 isomers (0.22%), HCFC-242 isomers (3.02%), HCFC-243 isomers (2.85%), HCFC-244 isomers (0.47%), HFC-245 isomers (1.07%), HCFO-1232zd (0.24%), HFO-1234ze(E) (1.00%), HFO-1234ze(Z) (0.25%), and heavy impurities (5.59%) is partially condensed to remove a stream containing new heavy impurities formed in the reaction and heavy impurities that could not be removed in the purge stream upstream of the reactor. The combined heavy impurities of these two streams may be disposed of by a suitable method, such as incineration, or may be subjected to further purification, such as vacuum, atmospheric, or superatmospheric distillation, to recover additional useful higher boiling fluorinated compounds which are recycled for further conversion in the reactor.

[0044] HCFO-1233zd(E)(54.22%), HCFO-1233zd(Z)(0.41%), HCFC-241 isomer(0.05%), HCFC-242 isomer(1.61%) , HCFC-243 isomer (2.33%), HCFC-244 isomer (0.46%), HFC-245 isomer (1.15%), HCFO-1232zd (0.21%), HFO-123 The product stream from the partial condenser, containing 4ze(E) (1.10%), HFO-1234ze(Z) (0.27%), as well as heavy impurities (0.93%), unconverted HF (1.0%), and HCl (36.26%), is passed to a distillation column where unconverted high boiling fluorinated compounds are removed and recycled to the bottoms stream, and unconverted HF and HCFO-1233zd and HCl products are removed in the overhead stream.

[0045] Example 2 Conversion of high boiling fluorinated components to 1233zd over fluorinated Cr2O3 catalysts A single pass unit was used for the reaction. The unit consisted of a feed delivery system, vaporizer, reactor, pressure controlled RCV, caustic solution scrubber, drying column, and PCC (product collection cylinder). A 2-inch Inconel 600 pipe type reactor was used. The reactor was heated by immersion in a sand bath. Five-point thermocouples were placed in the center of the catalyst bed to measure the process temperature. The distance between two adjacent probe points was 5 inches between the first two points and 4 inches thereafter.

[0046] One liter of fluorinated chromia (aka chromium oxyfluoride) catalyst was loaded into the reactor. The reactor was heated to the desired temperature under nitrogen. After the temperature stabilized, the organic and HF streams were fed to two steam vaporizers in series for vaporization, and the vaporized feed stream was fed to the bottom of the catalyst bed to start the reaction. The reactor effluent was sent to a caustic solution scrubber to remove acids and then to a drying column containing drierite before being collected in a cooled PCC. During operation, samples were periodically taken from the reactor outlet into a DI water-bearing gas bag for GC and GC-MS analysis. Prior to GC or GC-MS analysis of the liquid organic layer, the reactor effluent samples were cooled for 30 minutes, after which dichloromethane (DCM) was added to the bag and cooled for another 30 minutes.

[0047] The composition of the organic feed for the reaction is shown in Table 1 below.

[0048] [Table 1]

[0049] As can be seen, the sum of the HCFC-241, HCFC-242, and HCFC-243 isomers represented more than 92% of the total organic composition.

[0050] The reaction was carried out using fresh chromia catalyst. Other reaction conditions averaged over 266 hours are shown in Table 2.

[0051] [Table 2]

[0052] As shown in Table 2, the catalyst bed temperature was slightly lower than the sand bath temperature, indicating that the reaction was slightly endothermic in nature.

[0053] The conversions of HCFC-241, HCFC-242, and HCFC-243 over the 266 hour reaction time are shown in Table 3, along with the selectivities for lights, HCFO-1233zd(E), HCFO-1233zd(Z), and others. The lights included E-1,3,3,3-tetrafluoropropene (HFO-1234ze(E)), Z-1,3,3,3-tetrafluoropropene (HFO-1234ze(Z)), and 1,1,3,3-pentafluoropropane (HFC-245fa). Others included 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf), HCFO-1232, HCFO-1231, and HCO-1230 isomers, 1-chloro-1,3,3,3-tetrafluoropropane (HCFC-244fa), trichloropropene isomers, hexachloroethane, dimers such as C6H4F8 isomers, C6H3F7 isomers, C6H4F7Cl isomers, C6H3F6Cl isomers, C6H3F3Cl4 isomers, and unknown substances.

[0054] [Table 3]

[0055] As shown in Table 3, the selectivity and productivity of HCFO-1233zd(E) was approximately 90% and 8.6 lbs / h / ft 3 A reactor effluent sample was taken after 219 hours on stream for GC-MS analysis, and the results are shown in Table 4.

[0056] [Table 4] 1 Added externally for analysis.

[0057] HCFO-1233zd(E) was formed as the major component at 68.884%. Light components such as HFO-1234ze(E), HFC-245fa, and HFO-1234zeZ, as well as numerous other components such as HCFO-1233xf, HCFO-1232 isomers, HCFO-1231 isomers, HCO-1230 isomers, HCFC-244fa, trichloropropene isomers, hexachloroethane, dimers such as C6H4F8 isomers, C6H3F7 isomers, C6H4F7Cl isomers, C6H3F6Cl isomers, C6H3F3Cl4 isomers, and unknown substances were also formed as by-products.

[0058] Examples 3 to 27 Conversion of high boiling fluorinated components to 1233zd over other catalysts. Example 2 above is repeated, except that instead of the fluorinated Cr2O3 catalyst, other catalysts are used. Similar results are obtained in terms of yield and selectivity to produce E-1-chloro-3,3,3-trifluoropropene (HCFO-1233zd(E)).

[0059] [Table 5]

[0060] Example 28 Purging heavy impurities The process of FIG. 1 is carried out with heavy impurities purged from vaporizer 20 via stream 22 prior to reaction of vaporized stream 26 according to Examples 1 and 2 above.

[0061] The process of FIG. 1 is again carried out with heavy impurities purged from condenser 40 via stream 42 following reaction of vaporized stream 26 according to Examples 1 and 2 above.

[0062] The process of FIG. 1 is carried out with both heavy impurities purged from vaporizer 20 via stream 22 prior to reaction of vaporized stream 26 according to Examples 1 and 2 above, and heavy impurities purged from condenser 40 via stream 42 following reaction of vaporized stream 26 according to Examples 1 and 2 above.

[0063] Aspects Embodiment 1 is a process for converting a mixture of high-boiling fluorinated components to 1-chloro-3,3,3-trifluoropropene (HCFO-1233zd), comprising contacting the mixture with hydrogen fluoride (HF) to produce a combined reactant stream, vaporizing the combined reactant stream to produce a vaporized reactant stream, reacting the vaporized reactant stream in the presence of a catalyst to produce a product stream comprising E-1-chloro-3,3,3-trifluoropropene (HCFO-1233zd(E)) and heavy impurities, condensing at least a portion of the heavy impurities, and optionally purifying the product stream to produce E-1-chloro-3,3,3-trifluoropropene (HCFO-1233zd(E)).

[0064] Example 2 is the process of Example 1, wherein the high-boiling fluorinated component has a boiling point greater than 39°C.

[0065] Example 3 is the method of any of Examples 1 or 2, wherein the mixture of high-boiling fluorinated components comprises 1,1,3,3-tetrachloro-1-fluoropropane (HCFC-241fa), 1,3,3-trichloro-1,1-difluoropropane (HCFC-242fa), 1,1,3-trichloro-1,3-difluoropropane (HCFC-242fb), 3,3-dichloro-1,1,1-trifluoropropane (HCFC-243fa), 1,3-dichloro-1,1,3-trifluoropropane (HCFC-243fb), 3-chloro-1,1,1,3-tetrafluoropropane (HCFC-244fa), and combinations thereof.

[0066] Aspect 4 is the method of any one of Aspects 1 to 3, wherein the vaporization step is carried out at a temperature of 220° C. or greater.

[0067] Aspect 5 is the method of any one of Aspects 1 to 4, wherein the reacting step is carried out at a temperature between 200°C and 300°C.

[0068] A sixth aspect is the method of any one of the first to fifth aspects, wherein the condensing step is carried out at a temperature of 10° C. or greater.

[0069] Example 7 is the method of any one of Examples 1-6, wherein the catalyst is selected from the group consisting of chromium oxide, chromium oxyfluoride, and chromium halides.

[0070] Example 8 is the method of any one of Examples 1-7, wherein the catalyst is a chromium oxyfluoride catalyst.

[0071] Example 9 is the method of any one of Examples 1-8, wherein the composition further comprises a heavy impurity having a boiling point greater than 140°C.

[0072] Example 10 is the method of Example 9, wherein heavy impurities are purged from the vaporizer.

[0073] Example 11 is the process of either Example 9 or Example 10, wherein heavy impurities are purged from the partial condenser.

[0074] Example 12 is a process for converting a mixture of high-boiling fluorinated components to 1-chloro-3,3,3-trifluoropropene (HCFO-1233zd), comprising contacting the mixture with hydrogen fluoride (HF) to produce a combined reactant stream, vaporizing the combined reactant stream to produce a vaporized reactant stream and a heavy impurities stream, separating the heavy impurities stream from the vaporized reactant stream, reacting the vaporized reactant stream in the presence of a catalyst to produce a product stream comprising E-1-chloro-3,3,3-trifluoropropene (HCFO-1233zd(E)), and optionally purifying the product stream to produce E-1-chloro-3,3,3-trifluoropropene (HCFO-1233zd(E)).

[0075] Example 13 is the method of example 12, wherein the high-boiling fluorinated component has a boiling point greater than 39° C.

[0076] Example 14 is the method of any of Examples 12 or 13, wherein the mixture of high-boiling fluorinated components comprises 1,1,3,3-tetrachloro-1-fluoropropane (HCFC-241fa), 1,3,3-trichloro-1,1-difluoropropane (HCFC-242fa), 1,1,3-trichloro-1,3-difluoropropane (HCFC-242fb), 3,3-dichloro-1,1,1-trifluoropropane (HCFC-243fa), 1,3-dichloro-1,1,3-trifluoropropane (HCFC-243fb), 3-chloro-1,1,1,3-tetrafluoropropane (HCFC-244fa), and combinations thereof.

[0077] Example 15 is the method of any one of Examples 12 to 14, wherein the vaporization step is carried out at a temperature of 220° C. or greater.

[0078] Aspect 16 is the method of any one of Aspects 12 to 15, wherein the reacting step is carried out at a temperature between 200°C and 300°C.

[0079] Example 17 is the method of any one of Examples 12 to 16, wherein the condensing step is carried out at a temperature of 10° C. or greater.

[0080] Example 18 is the method of any one of Examples 12-17, wherein the catalyst is selected from the group consisting of chromium oxide, chromium oxyfluoride, and chromium halides.

[0081] Example 19 is the method of any one of Examples 12-18, wherein the catalyst is a chromium oxyfluoride catalyst.

[0082] Example 20 is the method of any one of Examples 12-19, wherein the heavy impurities stream comprises components having a boiling point greater than 140°C.

[0083] Aspect 21 is the process of any one of Aspects 1-11 or Aspects 12-20, wherein the vaporizing step is carried out at a temperature of 220° C. or greater, the condensing step is carried out at a temperature of 10° C. or greater, and the catalyst is chromium oxide.

[0084] Example 22 is the method of any of Examples 1-11 or Examples 12-20, wherein the catalyst is selected from alumina, iron oxide, magnesium oxide, zinc oxide, nickel oxide, cobalt oxide, aluminum fluoride, iron fluoride, magnesium fluoride, zinc fluoride, nickel fluoride, cobalt fluoride, fluorinated alumina, fluorinated iron oxide, fluorinated magnesium oxide, fluorinated nickel oxide, fluorinated cobalt oxide, titanium fluoride, molybdenum fluoride, aluminum oxyfluoride, and combinations thereof.

[0085] Example 23 is the method of any of Examples 1-11 or 12-20, wherein the catalyst is a zinc / chromium catalyst containing 0.5 to 6.0 wt. % Zn, based on the total weight of the catalyst.

[0086] Example 23 is the method of any of Examples 1-11 or 12-20, wherein the catalyst is a chromium catalyst having chromium (VI) oxide in an amount less than 1,000 ppm, less than 500 ppm, less than 150 ppm, or less than 100 ppm.

[0087] While the present disclosure has been described in terms of exemplary designs, the present disclosure may be further modified within the spirit and scope of the present disclosure, and this application is intended to cover such departures from the present disclosure as come within known or customary practice in the art to which the disclosure pertains.

Claims

1. 1. A process for converting a mixture of high-boiling fluorinated components to 1-chloro-3,3,3-trifluoropropene (HCFO-1233zd), comprising the steps of: contacting the mixture with hydrogen fluoride (HF) to produce a combined reactant stream; vaporizing the combined reactant stream to form a vaporized reactant stream; reacting the vaporized reactant stream in the presence of a catalyst to produce a product stream comprising E-1-chloro-3,3,3-trifluoropropene (HCFO-1233zd(E)) and heavy impurities; Concentrating at least a portion of the heavy impurities; Optionally purifying said product stream. A method comprising:

2. 2. The method of claim 1, wherein the high-boiling fluorinated component has a boiling point greater than 39°C.

3. 2. The method of claim 1, wherein the mixture of high-boiling fluorinated components comprises 1,1,3,3-tetrachloro-1-fluoropropane (HCFC-241fa), 1,3,3-trichloro-1,1-difluoropropane (HCFC-242fa), 1,1,3-trichloro-1,3-difluoropropane (HCFC-242fb), 3,3-dichloro-1,1,1-trifluoropropane (HCFC-243fa), 1,3-dichloro-1,1,3-trifluoropropane (HCFC-243fb), 3-chloro-1,1,1,3-tetrafluoropropane (HCFC-244fa), and combinations thereof.

4. 10. The method of claim 1, wherein the vaporization step is carried out at a temperature of 220°C or greater.

5. The method of claim 1, wherein the reacting step is carried out at a temperature of from 200° C. to 300° C.

6. 2. The process of claim 1, wherein the condensation step is carried out at a temperature of 10° C. or greater.

7. 2. The method of claim 1, wherein the catalyst is selected from the group consisting of chromium oxide, chromium oxyfluoride, and chromium halides.

8. 10. The method of claim 1, wherein the catalyst is a chromium oxyfluoride catalyst.

9. 10. The method of claim 1, wherein the composition further comprises heavy impurities having a boiling point greater than 140°C.

10. The following additional steps: purging the heavy impurities from the vaporizer; and purging said heavy impurities from the partial condenser. The method of claim 9 , further comprising at least one of:

11. The vaporization step is carried out at a temperature of 220° C. or higher, The condensation step is carried out at a temperature of 10° C. or higher; and The method of claim 1 , wherein the catalyst is chromium oxide.

12. 2. The method of claim 1, wherein the catalyst is a zinc / chromium catalyst containing 0.5 to 6.0 wt. % Zn, based on the total weight of the catalyst.

13. 1. A process for converting a mixture of high-boiling fluorinated components to 1-chloro-3,3,3-trifluoropropene (HCFO-1233zd), comprising the steps of: contacting the mixture with hydrogen fluoride (HF) to produce a combined reactant stream; vaporizing the combined reactant stream to produce a vaporized reactant stream and a heavy impurity stream; separating said heavy impurities stream from said vaporized reactant stream; reacting the vaporized reactant stream in the presence of a catalyst to produce a product stream comprising E-1-chloro-3,3,3-trifluoropropene (HCFO-1233zd(E)); Optionally purifying said product stream. A method comprising:

14. 14. The method of claim 13, wherein the high-boiling fluorinated component has a boiling point greater than 39°C.

15. 14. The method of claim 13, wherein the mixture of high-boiling fluorinated components comprises 1,1,3,3-tetrachloro-1-fluoropropane (HCFC-241fa), 1,3,3-trichloro-1,1-difluoropropane (HCFC-242fa), 1,1,3-trichloro-1,3-difluoropropane (HCFC-242fb), 3,3-dichloro-1,1,1-trifluoropropane (HCFC-243fa), 1,3-dichloro-1,1,3-trifluoropropane (HCFC-243fb), 3-chloro-1,1,1,3-tetrafluoropropane (HCFC-244fa), and combinations thereof.

16. 14. The method of claim 13, wherein the vaporization step is carried out at a temperature of 220° C. or greater.

17. The method of claim 13, wherein the reacting step is carried out at a temperature of from 200° C. to 300° C.

18. 14. The method of claim 13, wherein the condensing step is carried out at a temperature of 10° C. or greater.

19. 14. The method of claim 13, wherein the catalyst is selected from the group consisting of chromium oxide, chromium oxyfluoride, and chromium halides.

20. 14. The method of claim 13, wherein the catalyst is a chromium oxyfluoride catalyst.

Images