Manufacturing method of HCFO-1233zd

Abstract

To provide a method for allowing a partially fluorinated intermediate to be converted into a target product, namely, HCFO-1233zd.SOLUTION: A process for production of HCFO-1233zd comprises the steps of: (i) providing partially fluorinated propane feedstock selected from tetrachlorofluoropropanes, trichlorodifluoropropanes, dichlorotrifluoropropanes, and a mixture thereof; (ii) reacting the feedstock in a vapor phase reactor in the presence of HF and in the presence of a solid catalyst under conditions effective for forming a product stream comprising HCFO-1233zd isomers, HCl and unconverted starting materials; (iii) recovering or removing HCl and HF, and (iv) isolating HCFO-1233zd(E), HCFO-1233zd(Z), or both.SELECTED DRAWING: None

Description

[Technical Field]

[0001] This application claims domestic priority to co-pending U.S. Provisional Patent Application No. 62 / 160,021, filed May 12, 2015, the disclosure of which is incorporated herein by reference.

[0002] The present invention relates to a process for producing hydrochlorofluoroolefins (HCFOs), particularly trans-1-chloro-3,3,3-trifluoropropene (HCFO-1233zd(E)). [Background technology]

[0003] Chlorofluorocarbon (CFC)-based chemicals are widely used in industry for a variety of different applications, including as refrigerants, aerosol propellants, blowing agents, and solvents, among others. However, some CFCs are believed to deplete the Earth's ozone layer. Therefore, more environmentally friendly alternatives to CFCs have been introduced. For example, 1,1,1,3,3-pentafluoropropane (HFC-245fa) has been recognized as having favorable physical properties for several industrial applications, such as foam blowing agents and solvents, and is therefore considered a good replacement for the CFCs previously used for these applications. Unfortunately, the use of some hydrofluorocarbons, such as HFC-245fa, in industrial applications is now believed to contribute to global warming. Therefore, more environmentally friendly alternatives to hydrofluorocarbons are currently being sought.

[0004] The compound 1-chloro-3,3,3-trifluoropropene, also known as HCFO-1233zd or simply 1233zd, is a candidate to replace HFC-245fa in several applications, such as use as a blowing agent and solvent. 1233zd has two isomers with different physical properties. As one example of the different properties between the two isomers, 1233zd(Z) has a boiling point of about 38°C, while 1233zd(E) has a boiling point of about 19°C. In some applications, pure 1233zd(E), pure 1233zd(Z), certain blends of the (Z) and (E) isomers, or the isomers of 1233zd are preferred. It may be desirable to use either one or both of these isomers with specific blends of other compounds to control the solution properties. For example, in some solvent applications, it is desirable to have a relatively high boiling point. In some such applications, pure 1233zd(Z) may have more desirable physical properties (e.g., a higher boiling point) than either pure 1233zd(E) or a mixture of the two 1233zd isomers.

[0005] Methods for synthesizing 1233zd are known. For example, PCT Publication WO-97 / 24307 discloses a method for producing 1233zd by the vapor-phase reaction of 1,1,1,3,3-pentachloropropane (HCC-240fa) with hydrogen fluoride (HF). However, this process produces 1233zd in relatively low yield.

[0006] U.S. Patent 6,844,475 describes the catalytic liquid-phase reaction of HCC-240fa with HF to produce 1233zd in higher yields. However, the presence of a fluorination catalyst promotes the formation of heavy by-products, oligomers, and tars, which can accumulate in the reactor over time, causing catalyst dilution and deactivation, and resulting in productivity losses due to excessive downtime required to periodically remove these by-products from the reactor.

[0007] U.S. Patent 8,704,017 discloses the non-catalytic liquid-phase reaction of HCC-24fa with HF to reduce the formation of heavy by-products. However, one drawback of not using a catalyst is that the reaction rate is slower and a significant amount of stable under-fluorinated intermediates may be formed, including tetrachlorofluoropropanes such as 1,1,3,3-tetrachloro-1-fluoropropane (HCFC-241fa), trichlorodifluoropropanes such as 1,3,3-trichloro-1,1-difluoropropane (HCFC-242fa) and 1,1,3-trichloro-1,3-difluoropropane (HCFC-242fb), and dichlorotrifluoropropanes such as 1,1-dichloro-3,3,3-trifluoropropane (HCFC-243fa) and 1,3-dichloro-1,1,3-trifluoropropane (HCFC-243fb), which significantly reduces the single-pass productivity of HCFC-1233zd.

[0008] U.S. Patent 9,045,386 describes a method for producing trans-1-chloro-3,3,3-trifluoropropene (HCFO-1233zd(E)) in high purity on a commercial scale, and is incorporated herein by reference. [Prior art documents] [Patent documents]

[0009] [Patent Document 1] PCT Publication No. WO-97 / 24307 [Patent Document 2] U.S. Patent 6,844,475 [Patent Document 3] U.S. Patent 8,704,017 [Patent Document 4] U.S. Patent 9,045,386 Summary of the Invention [Problem to be solved by the invention]

[0010] Based on the above, there remains a need for a means by which the partially fluorinated intermediate can be converted to the target product, i.e., HCFO-1233zd. The present invention satisfies this need. [Means for solving the problem]

[0011] The present invention provides a method for producing 1-chloro-3,3,3-trifluoropropene (HCFO-1233zd). The method generally comprises the following four steps: (1) providing a feedstock comprising tetrachlorofluoropropane, trichlorodifluoropropane, and dichlorotrifluoropropane; (2) reacting the feedstock in the presence of HF and in the presence of a solid catalyst in a vapor phase reactor under conditions effective to form a product stream comprising HCFO-1233zd, HCl, and unconverted starting materials; (3) recovering or removing the HCl and HF; and (4) isolating HCFO-1233zd(E), HCFO-1233zd(Z), or both; The process includes:

[0012] Non-limiting examples of tetrachlorofluoropropanes include, but are not limited to, 1,1,3,3-tetrachloro-1-fluoropropane (HCFC-241fa). Non-limiting examples of trichlorodifluoropropanes include, but are not limited to, 1,3,3-trichloro-1,1-difluoropropane (HCFC-242fa) and 1,1,3-trichloro-1,3-difluoropropane (HCFC-242fb). Non-limiting examples of dichlorotrifluoropropanes include, but are not limited to, 1,1-dichloro-3,3,3-trifluoropropane (HCFC-243fa) and 1,3-dichloro-1,1,3-trifluoropropane (HCFC-243fb). A preferred feedstock comprises a mixture of HCFC-241, HCFC-242 and HCFC-243 (HCFC-242 / HCFC-243).

[0013] In some embodiments, the feedstock comprises a total of at least 50 wt. % tetrachlorofluoropropane, trichlorodifluoropropane, and dichlorotrifluoropropane, preferably at least 80 wt. %, more preferably at least 90 wt. %, and most preferably at least 95 wt. % tetrachlorofluoropropane, trichlorodifluoropropane, and dichlorotrifluoropropane.

[0014] In some embodiments, the solid catalyst may be one or more of a metal oxide halide in bulk or supported form, a metal halide in bulk or supported form, and a carbon-supported transition metal. Suitable catalysts non-exclusively include metal oxide halide (e.g., fluorinated Cr2O3, fluorinated Al2O3, fluorinated MgO), metal halides (e.g., CrF3, AlF3, AlCl3, FeCl3, FeCl3 / C), and carbon-supported transition metals (zero oxidation state), such as Fe / C, Co / C, Ni / C, and Pd / C.

[0015] Thus, one aspect of the present invention is a method for producing a cellulose acetate ester comprising the steps of: providing a feedstock comprising tetrachlorofluoropropane, trichlorodifluoropropane, and dichlorotrifluoropropane; reacting the feedstock in the presence of anhydrous HF and in the presence of a solid catalyst in a vapor phase reactor under conditions effective to form a product stream comprising HCFO-1233zd, HCl, and unconverted starting materials; recovering or removing the HCl and HF; and isolating HCFO-1233zd(E), HCFO-1233zd(Z), or both; The present invention provides a method for producing a chlorofluoroalkene, comprising the steps of:

[0016] Another aspect of the present invention is a method for producing a method of manufacturing a semiconductor device comprising the steps of: providing a feedstock comprising tetrachlorofluoropropane, trichlorodifluoropropane, and dichlorotrifluoropropane; reacting the feedstock in the presence of a solid catalyst in a vapor phase reactor under conditions effective to form a product stream comprising HCFO-1233zd, HCl, and unconverted starting materials; recovering or removing the HCl and HF; and isolating HCFO-1233zd(E), HCFO-1233zd(Z), or both; The present invention provides a method for producing a chlorofluoroalkene, comprising the steps of:

[0017] It will be recognized by those skilled in the art to which this invention pertains that any feature described herein with respect to any particular aspect and / or embodiment of the invention may be combined with any other feature or features of any other aspect and / or embodiment of the invention described herein, modifications necessary to ensure compatibility of the combination, and such combinations are considered to be part of the invention contemplated by this disclosure.

[0018] It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the invention as claimed. Other embodiments will become apparent to those skilled in the art from consideration of the specification and practice of the invention disclosed therein. DETAILED DESCRIPTION OF THE INVENTION

[0019] As indicated above, the present invention provides providing a feedstock comprising tetrachlorofluoropropane, trichlorodifluoropropane, and dichlorotrifluoropropane; reacting the feedstock in the presence of HF and in the presence of a solid catalyst in a vapor phase reactor under conditions effective to form a product stream comprising HCFO-1233zd, HCl, and unconverted starting materials; and isolating HCFO-1233zd(E), HCFO-1233zd(Z), or both; The present invention relates to a method for producing 1233zd, which includes:

[0020] In some embodiments, the feedstock comprises a total of at least 50 wt%, preferably at least 80 wt%, more preferably at least 90 wt%, and most preferably at least 95 wt% of tetrachlorofluoropropane, trichlorodifluoropropane, and dichlorotrifluoropropane. Non-limiting examples of tetrachlorofluoropropanes include, but are not limited to, 1,1,3,3-tetrachloro-1-fluoropropane (HCFC-241fa). Non-limiting examples of trichlorodifluoropropanes include, but are not limited to, 1,3,3-trichloro-1,1-difluoropropane (HCFC-242fa) and 1,1,3-trichloro-1,3-difluoropropane (HCFC-242fb). Non-limiting examples of dichlorotrifluoropropanes include, but are not limited to, 1,1,-dichloro-3,3,3-trifluoropropane (HCFC-243fa) and 1,3-dichloro-1,1,3-trifluoropropane (HCFC-243fb).

[0021] In a preferred embodiment, distillation is used to isolate tetrachlorofluoropropane, trichlorodifluoropropane, and dichlorotrifluoropropane from a product stream containing HCFO-1233zd(E), HCFO-1233zd(Z), HCFC-241fa, HCFC-242fa, HCFC-242fb, HCFC-243fa, and HCFC-243fb. These intermediates can be isolated as individual compounds or as a mixture. As disclosed in U.S. Patent 8,835,700, such a product stream can be obtained by reacting HCC-240fa with anhydrous HF in a liquid-phase reactor in the absence of a catalyst. This patent is incorporated herein by reference.

[0022] The reaction of tetrachlorofluoropropane (HCFC-241), trichlorodifluoropropane (HCFC-242), and dichlorotrifluoropropane (HCFC-243) can be carried out in any suitable reaction vessel or reactor, preferably constructed of a material resistant to the corrosive effects of hydrogen fluoride, such as nickel and its alloys, such as Hastelloy, Inconel, Incoloy, and Monel, or vessels lined with fluoropolymers. These may be single pipes or multiple tubes filled with solid catalyst. Three types of catalysts can be used: (1) bulk or supported metal halides, (2) bulk or supported metal oxide halides, and (3) bulk or supported zero-valent metals. Useful catalysts non-exclusively include fluorinated Cr2O3, fluorinated Al2O3, fluorinated MgO, CrF3, AlF3, AlCl3, FeCl3, MgF2, FeCl3 / C, and carbon-supported transition metals (zero oxidation state) such as Fe / C, Co / C, Ni / C, and Pd / C. The HCFC-242 / HCFC-243 feed stream is introduced into the reactor either in pure form, impure form, or with an optional inert gas diluent such as nitrogen, argon, or the like.

[0023] In some embodiments of the present invention, the HCFC-241 / HCFC-242 / HCFC-243 feed is prevaporized or preheated prior to introduction into the reactor. Alternatively, the HCFC-241 / HCFC-242 / HCFC-243 feed stream is vaporized inside the reactor. Useful reaction temperatures can range from about 200°C to about 600°C. A preferred temperature is about 25°C. The temperature may range from 0°C to about 450°C, with a more preferred temperature range being from about 300°C to about 350°C. The reaction may be carried out at atmospheric pressure, superatmospheric pressure, or under vacuum. The vacuum pressure may be from about 5 Torr to about 760 Torr. The contact time between the HCFC-241 / HCFC-242 / HCFC-243 feed stream and the catalyst may range from about 0.5 seconds to about 120 seconds, although longer or shorter times may be used.

[0024] In a preferred embodiment, HF is co-fed to the reactor along with the HCFC-241 / HCFC-242 / HCFC-243 feed stream. The HF is pre-vaporized or pre-heated before entering the reactor. Alternatively, the HF is vaporized inside the reactor. Applicants have unexpectedly discovered that the presence of the HF co-feed stream significantly suppresses the formation of several undesirable by-products, including, but not limited to, dichlorodifluoropropenes (isomers of HCFO-1232), trichlorofluoropropenes (isomers of HCFO-1231), tetrachloropropenes (isomers of HCFO-1230), and the like. The molar ratio of HF to organic compound can range from 0.01:1 to 10:1, preferably from 0.1:1 to 5:1, and more preferably from 0.5:1 to 3:1.

[0025] In preferred embodiments, the process flow is either downward or upward through the catalyst bed. It may also be advantageous to periodically regenerate the catalyst while it is in place in the reactor after extended use. Catalyst regeneration can be accomplished by any means known in the art, such as by passing air or air diluted with nitrogen over the catalyst at temperatures of about 200°C to about 500°C, preferably about 300°C to about 400°C, for about 0.5 hours to about 3 days. This is followed by H2 treatment at temperatures of about 100°C to about 400°C, preferably about 200°C to about 300°C, for supported transition metal catalysts, or HF treatment at temperatures of about 200°C to about 600°C, preferably about 300°C to about 400°C, for metal halide oxide catalysts and metal halide catalysts.

[0026] The reaction typically produces a reaction product containing HCFO-1233zd and one or more compounds other than HCFO-1233zd. The reaction product typically takes the form of a mixture of the following: unreacted starting materials, such as isomers of HCFC-241, HCFC-242, and HCFC-243, and HF if HF is co-fed; the target product, such as HCFO-1233zd; and by-products, such as HCl, HF, HFO-1234ze, HFC-245fa, HCFC-244fa, isomers of HCFO-1232, isomers of HCFO-1231, isomers of HCFO-1230, etc.

[0027] The desired level of feedstock conversion and HCFO-1233zd selectivity can be influenced by operating parameters such as reaction temperature, pressure, and residence time. The reaction is conducted under conditions sufficient to achieve the formation of the target product. The selectivity to HCFC-1233zd (total of the two isomers) using the preferred catalyst is about 50% or greater, more preferably about 70% or greater, and most preferably about 90% or greater. The feedstock conversion is preferably about 10% or greater, more preferably about 40% or greater, and most preferably about 70% or greater.

[0028] HCFC-1233zd can be recovered from the reaction product as either or both of its E and Z isomers. Recovery of compounds from the reaction product can be accomplished by any means known in the art, such as extraction and preferably by distillation. For example, distillation can be carried out in a standard distillation column at pressures below about 300 psig, preferably below about 150 psig, and most preferably below 100 psig. The pressure of the distillation column inherently determines the distillation operating temperature. HCl can be recovered by operating the distillation column at about -40°C to about 25°C, preferably about -40°C to about -20°C. HCFO-1233zd can be recovered by operating the distillation column at about -10°C to about 60°C. The HCFO-1233zd(E) and HCFO-1233zd(Z) can be recovered by distillation using a single or multiple distillation columns. If desired, HCFO-1233zd(E) and HCFO-1233zd(Z) can be separated from each other by means known in the art, such as extraction and distillation.

[0029] In a preferred embodiment, HCl is removed from the reaction product. More preferably, HCl is removed before HCFC-1233zd is recovered from the reaction product mixture. HCl in the product stream is recovered using an HCl column. High-purity HCl is isolated from the top of the column and absorbed as concentrated HCl in deionized water. Alternatively, HCl can be recovered or removed from the product stream by using a water or caustic scrubber. When a water extractor is used, aqueous HCl solutions of various concentrations are formed. When a caustic scrubber is used, HCl is neutralized as a chloride salt in aqueous solution.

[0030] In some embodiments, the substantially HCl-free organic compound / HF mixture is fed to a sulfuric acid extractor or phase separator to remove HF from the mixture. The HF is either dissolved in the sulfuric acid or phase separated from the organic mixture. For embodiments using a sulfuric acid adsorption system, sulfuric acid is preferably added so that the weight ratio of sulfuric acid to hydrogen fluoride is in the range of about 1:1 to about 10:1. More preferably, this weight ratio is in the range of about 1:1 to about 8:1, and most preferably about 2:1 to about 4:1. The HF is then desorbed from the sulfuric acid / HF mixture by stripping distillation and recycled back to the fluorination reactor. For embodiments using a phase separator, the extraction is preferably carried out at a temperature of about -20°C to about 100°C, more preferably about -10°C to about 60°C, and most preferably about 0°C to about 40°C. The HF is then phase separated and recycled back to the reactor. The organic mixture from either the sulfuric acid extractor overhead or the phase separator bottoms may need to be treated (scrubbed or adsorbed) to remove traces of HF before sending it to the next unit operation for product isolation.

[0031] In some embodiments, the isomeric HCFO-1233zd(E) and HCFO-1233zd(Z) are isolated as two products. The acid-free crude product is first sent to a distillation column, from which HCFO-1233zd(E) exits the top of the column along with some lighter components having a boiling point lower than that of HCFO-1233zd(E), while HCFO-1233zd(Z) exits the bottom of the column along with some heavier components having a boiling point higher than that of HCFO-1233zd(Z). The overhead and bottom streams are then sent to two separate columns for further purification to obtain the HCFO-1233zd(E) and HCFO-1233zd(Z) products. [Example]

[0032] The following examples are provided to further illustrate the present invention and should not be construed as limiting thereof. Example 1: In this example, 5 wt% FeCl3 / carbon was used as the catalyst. A 3 / 4" x 0.035" tubular Inconel 625 reactor was used. The reactor was installed in the center of a three-zone electric furnace. The process temperature was recorded using a multipoint thermocouple placed within the catalyst bed inside the reactor. The distance between two adjacent probe points was 4 inches. 40 mL of solid catalyst was loaded so that the bed was inside three adjacent probe points. The reactor was heated to the desired temperature in a nitrogen stream, and then a 51.6 GC area % 243 (two isomers, with 243fb being the major component) / 47.5 GC area % 242fa feed stream was fed into the bottom of the vertically mounted reactor to start the reaction. The reaction effluent was periodically tested for its composition.

[0033] As shown in Table 1, the percentage of 1233zd (1233zd-E + 1233zd-Z) in the vapor and liquid phases was about 33% and about 2.5%, respectively.

[0034] [Table 1]

[0035] Example 2: In this example, fluorinated Cr2O3 was used as the catalyst. A 3 / 4" x 0.035" tubular Inconel 625 reactor was used. The reactor was installed in the center of a three-zone electric furnace. The process temperature was recorded using a multipoint thermocouple placed within the catalyst bed inside the reactor. The distance between two adjacent probe points was 4 inches. 20 mL of solid catalyst was loaded so that the bed was inside the two adjacent probe points. The reactor was heated to the desired temperature in a nitrogen stream, and then a 51.6 GC area % 243 (two isomers, with 243fb being the major component) / 47.5 GC area % 242fa feed stream was fed into the bottom of the vertically mounted reactor to start the reaction. The reaction effluent was periodically tested for its composition. As shown in Table 2, the percentage of 1233zd (1233zd-E + 1233zd-Z) in the vapor and liquid phases was about 81% and about 35%, respectively.

[0036] [Table 2]

[0037] Example 3: In this example, the same fluorinated Cr2O3 catalyst as in Example 2 was used. A 3 / 4" x 0.035" tubular Inconel 625 reactor was used. The reactor was installed in the center of a three-zone electric furnace. The process temperature was recorded using a multipoint thermocouple placed within the catalyst bed inside the reactor. The distance between two adjacent probe points was 4 inches. 20 mL of solid catalyst was loaded so that the bed was inside the two adjacent probe points. The reactor was heated to the desired temperature in a nitrogen stream, and then a 51.6 GC area % 243 (two isomers, with 243fb being the major component) / 47.5 GC area % 242fa feed stream and anhydrous HF were fed into the bottom of the vertically mounted reactor to start the reaction. The reaction effluent was periodically tested for its composition.

[0038] Applicants unexpectedly found that co-feeding significantly reduced the amount of 1230 isomer produced to below 1% (versus about 18% in the absence of HF), while It was found that the amount of 1233zd remaining in the samples was almost the same.

[0039] As used herein, the singular forms "a," "an," and "the" include the plural unless the context clearly dictates otherwise. Furthermore, when an amount, concentration, or other value or parameter is given as either a range, a preferred range, or a list of higher and lower preferred values, this should be understood to specifically disclose all ranges formed from any pairing of any higher range limit or preferred value with any lower range limit or preferred value, regardless of whether the ranges are separately disclosed. When a range of numerical values ​​is given in the specification, unless otherwise indicated, it is intended that the range include its endpoints, and all integers and decimals within the range. It is not intended that the scope of the invention be limited to the specific values ​​given when defining a range.

[0040] It should be understood that the above description is only illustrative of the present invention. Various alternatives and modifications can be thought of by those skilled in the art without departing from the present invention. Accordingly, the present invention is intended to embrace all such alternatives, modifications, and variations that fall within the scope of the appended claims. This specification includes the following aspects of the invention. [1] (i) providing a propane feedstock selected from the group consisting of tetrachlorofluoropropane, trichlorodifluoropropane, dichlorotrifluoropropane, and mixtures thereof; (ii) reacting in a vapor phase reactor a propane feedstock in the presence of HF and in the presence of a solid catalyst under conditions effective to form a product stream comprising isomers of HCFO-1233zd, HCl, and unconverted starting material; (iii) recovering or removing the HCl and HF; and (iv) isolating the HCFO-1233zd-E isomer, the HCFO-1233zd-Z isomer, or both compounds; A method for producing 1-chloro-3,3,3-trifluoropropene (HCFO-1233zd), comprising the steps of: [2] The method of claim 1, wherein the propane in the feedstock comprises 1,1,3,3-tetrachloro-1-fluoropropane (HCFC-241fa). [3] The method of claim 1, wherein the propane in the feedstock comprises 1,3,3-trichloro-1,1-difluoropropane (HCFC-242fa). [4] The method of claim 1, wherein the propane in the feedstock comprises 1,1,3-trichloro-1,3-difluoropropane (HCFC-242fb). [5] The method of claim 1, wherein the propane in the feedstock comprises 1,1-dichloro-3,3,3-trifluoropropane (HCFC-243fa). [6] The method of claim 1, wherein the propane in the feedstock comprises 1,3-dichloro-1,1,3-trifluoropropane (HCFC-243fb). [7] The catalyst is fluorinated Cr 2 O 3 , fluorinated Al 2 O 3 The method according to [1], comprising one or more halogenated metal oxides selected from the group consisting of: [8] The catalyst is CrF 3 , AlF 3 , AlCl 3 , FeCl 3 , and FeCl 3 The method according to [1], wherein the metal halide is one or more metal halides selected from the group consisting of: [9] 10. The method of claim 1, wherein the catalyst comprises one or more carbon-supported zero-oxidation state transition metals selected from the group consisting of Fe / C, Co / C, Ni / C, and Pd / C.

[10] The method according to [1], wherein the molar ratio of HF to propane in the feed is in the range of 0.01:1 to 10:1.

Claims

1. (i) providing a subfluorinated propane feedstock selected from the group consisting of tetrachlorofluoropropane, trichlorodifluoropropane, dichlorotrifluoropropane, and mixtures thereof; (ii) reacting in a vapor phase reactor a subfluorinated propane feed in the presence of HF and in the presence of a solid catalyst under conditions effective to form a product stream comprising isomers of HCFO-1233zd, HCl, and unconverted starting material, wherein the molar ratio of HF to propane in the subfluorinated propane feed is in the range of 0.5:1 to 3:1; (iii) recovering or removing the HCl and HF; and (iv) isolating the HCFO-1233zd-E isomer, or separately isolating both the HCFO-1233zd-E isomer and the HCFO-1233zd-Z isomer, wherein the isolating comprises distilling the product stream in a distillation column to provide an overhead stream comprising the HCFO-1233zd-E isomer and a bottoms stream comprising the HCFO-1233zd-Z isomer; 1. A method for producing 1-chloro-3,3,3-trifluoropropene (HCFO-1233zd), comprising the steps of: (a) Fluorinated Cr ２ O ３ , fluorinated Al ２ O ３ and one or more halogenated metal oxides selected from the group consisting of fluorinated MgO, or (b) CrF ３ , AlF ３ , AlCl ３ , FeCl ３ , and FeCl ３ / C The method comprising:

2. The catalyst is fluorinated Cr ２ O ３ The method of claim 1 , comprising:

3. 10. The method of claim 1, wherein the HF is dissolved in sulfuric acid using a sulfuric acid adsorption system or removed by phase separation.

4. 10. The process of claim 1, wherein the subfluorinated propane feedstock is pre-vaporized or pre-heated prior to being introduced into the vapor phase reactor.

5. The method of claim 1, wherein the reaction temperature is from 200°C to 600°C.

6. 10. The process of claim 1, wherein the contact time between the subfluorinated propane feed and the catalyst is from 0.5 seconds to 120 seconds.

7. 10. The process of claim 1, further comprising purifying the overhead and bottoms streams to obtain purified HCFO-1233zd-E isomers and purified HCFO-1233zd-Z isomers.

8. 10. The method of claim 1, wherein the partially fluorinated propane feedstock comprises dichlorotrifluoropropane (HCFC-243) and 1,3,3-trichloro-1,1-difluoropropane (HCFC-242fa).

9. 10. The process of claim 1, wherein the propane in the partially fluorinated propane feed comprises 1,1,3,3-tetrachloro-1-fluoropropane (HCFC-241fa).

10. 10. The process of claim 1, wherein the propane in the partially fluorinated propane feed comprises 1,3,3-trichloro-1,1-difluoropropane (HCFC-242fa).

11. 10. The process of claim 1, wherein the propane in the partially fluorinated propane feed comprises 1,1,3-trichloro-1,3-difluoropropane (HCFC-242fb).

12. 10. The process of claim 1, wherein the propane in the partially fluorinated propane feed comprises 1,1-dichloro-3,3,3-trifluoropropane (HCFC-243fa).

13. 10. The process of claim 1, wherein the propane in the partially fluorinated propane feed comprises 1,3-dichloro-1,1,3-trifluoropropane (HCFC-243fb).

14. 10. The method of claim 1, wherein the reaction is carried out under a pressure selected from the group consisting of atmospheric pressure, superatmospheric pressure, and vacuum, and the vacuum pressure may be from about 5 Torr to about 760 Torr.

15. The method of claim 1, wherein the reaction temperature is 250°C to 450°C.

16. The method of claim 1, wherein the reaction temperature is 300°C to 350°C.

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