PROCESS FOR MAKING 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), in particular 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, such 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 are being introduced. For example, 1,1,1,3,3-pentafluoropropane (HFC-245fa) is recognized as having favorable physical properties for some industrial applications, such as foam blowing agents and solvents, and is therefore considered to be a good alternative to 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 some 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., whereas 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 may be used. In some applications, it may be desirable to use either one or both of the isomers, together with certain blends of other compounds to control the solution properties. For example, in some solvent applications, it may be 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] US 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 the fluorination catalyst promotes the formation of heavy by-products, oligomers, and tars that can accumulate in the reactor over time, causing catalyst dilution and deactivation, and resulting in lost productivity due to excessive downtime to periodically remove these by-products from the reactor.

[0007] In US Patent 8,704,017, it is disclosed that HCC-24fa is reacted with HF in a non-catalytic liquid phase 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 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) may be formed, which greatly 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 in a vapor phase reactor the feedstock in the presence of HF and in the presence of a solid catalyst 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% by weight of tetrachlorofluoropropane, trichlorodifluoropropane, and dichlorotrifluoropropane, preferably at least 80% by weight, more preferably at least 90% by weight, and most preferably at least 95% by weight.

[0014] In some embodiments, the solid catalyst may be one or more of halide metal oxides in bulk or supported form, metal halides in bulk or supported form, and carbon-supported transition metals. Suitable catalysts non-exclusively include halide metal oxides (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 medicament 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 process for producing a method for producing 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 the 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 PREFERRED EMBODIMENTS

[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 at least 50% by weight, preferably at least 80% by weight, more preferably at least 90% by weight, and most preferably at least 95% by weight of tetrachlorofluoropropane, trichlorodifluoropropane, and dichlorotrifluoropropane. Non-limiting examples of tetrachlorofluoropropane include, but are not limited to, 1,1,3,3-tetrachloro-1-fluoropropane (HCFC-241fa). Non-limiting examples of trichlorodifluoropropane 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 mixtures. As disclosed in U.S. Patent 8,835,700, such product streams 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 materials resistant to the corrosive action of hydrogen fluoride, such as nickel and its alloys, such as Hastelloy, Inconel, Incoloy, and Monel, or vessels lined with fluoropolymers. These can be single pipes or multiple tubes filled with solid catalyst. Three types of catalysts can be used, including (1) bulk or supported metal halides, (2) bulk or supported metal halide oxides, 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 in either pure form, impure form, or with an optional inert gas diluent such as nitrogen, argon, and the like.

[0023] In some embodiments of the present invention, the HCFC-241 / HCFC-242 / HCFC-243 feed streams are prevaporized or preheated prior to introduction into the reactor. Alternatively, the HCFC-241 / HCFC-242 / HCFC-243 feed streams are 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., more preferably from about 300° C. to about 350° C. The reaction may be carried out at atmospheric pressure, above atmospheric pressure, or under vacuum. The vacuum pressure may be from about 5 Torr to about 760 Torr. Contact time of the HCFC-241 / HCFC-242 / HCFC-243 feed stream with 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 with the HCFC-241 / HCFC-242 / HCFC-243 feed streams. HF is pre-vaporized or pre-heated prior to introduction into the reactor. Alternatively, HF is vaporized inside the reactor. Applicants have unexpectedly found that the presence of the HF co-feed stream can significantly suppress the formation of several undesirable by-products, such as non-exclusively dichlorodifluoropropenes (isomers of HCFO-1232), trichlorofluoropropenes (isomers of HCFO-1231), tetrachloropropenes (isomers of HCO-1230), and the like. The molar ratio of HF / organic compounds may 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 a preferred embodiment, the process flow is either downward or upward through the bed of catalyst. It may also be advantageous to periodically regenerate the catalyst while it is in place in the reactor after extended use. The catalyst may be regenerated by any means known in the art, for example by passing air or air diluted with nitrogen over the catalyst at a temperature 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 a temperature 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 a temperature of about 200°C to about 600°C, preferably about 300°C to about 400°C for halide metal oxide catalysts and metal halide catalysts.

[0026] The reaction produces a reaction product that typically includes 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 HCO-1230, etc.

[0027] The desired level of feed conversion and selectivity to HCFO-1233zd can be influenced by operating parameters such as conditions such as reaction temperature, pressure, and residence time. The reaction is conducted at conditions sufficient to achieve formation of the target product. The selectivity to HCFC-1233zd (total of 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 conversion of the feed 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 the compounds from the reaction product can be accomplished by any means known in the art, such as extraction and preferably distillation. For example, distillation can be accomplished 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 in a single column or multiple 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 chloride salts in aqueous solution.

[0030] In some embodiments, the substantially HCl-free organic / HF mixture is fed to a sulfuric acid extractor or phase separator to remove HF from the mixture. HF is 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 such that the weight ratio of sulfuric acid to hydrogen fluoride is in the range of about 1:1 to about 10:1. More preferably, the weight ratio is in the range of about 1:1 to about 8:1, and most preferably, about 2:1 to about 4:1. 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. 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 it is sent to the next unit operation for product isolation.

[0031] In some embodiments, the isomers HCFO-1233zd(E) and HCFO-1233zd(Z) are isolated as two products. The acid-free crude product is first sent to a distillation column, and then HCFO-1233zd(E) exits the top of the column along with some light components having a lower boiling point than HCFO-1233zd(E), while HCFO-1233zd(Z) exits the bottom of the column along with some heavy components having a higher boiling point than 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. EXAMPLES

[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 catalyst. A 3 / 4" x 0.035" tube 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 multi-point thermocouple placed in 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 flow, and then a 51.6 GC area % 243 (two isomers, 243fb was 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 stream was periodically tested for its composition.

[0033] As shown in Table 1, the percentage of 1233zd (1233zd-E + 1233zd-Z) in the vapor phase and in the liquid phase 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" tube type 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 multi-point thermocouple placed in 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 flow, and then a 51.6 GC area % 243 (two isomers, 243fb was 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 stream was periodically tested for its composition. As shown in Table 2, the percentage of 1233zd (1233zd-E + 1233zd-Z) in the vapor phase and in the liquid phase 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" tube type 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 multi-point thermocouple placed in 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 flow, and then a 51.6 GC area % 243 (two isomers, 243fb was 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 stream 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

[0039] As used herein, the singular forms "a", "an" and "the" include the plural unless the description clearly indicates 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 pair of any higher range limit or preferred value and 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, the range is intended to include its endpoints and all integers and decimals within the range. It is not intended to limit the scope of the invention to the specific values ​​given in defining the 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.

Claims

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 materials; (iii) recovering or removing 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. 2. The process of claim 1, wherein the propane in the feed comprises 1,1,3,3-tetrachloro-1-fluoropropane (HCFC-241fa).

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

4. 2. The process of claim 1, wherein the propane in the feed comprises 1,1,3-trichloro-1,3-difluoropropane (HCFC-242fb).

5. 2. The process of claim 1, wherein the propane in the feed comprises 1,1-dichloro-3,3,3-trifluoropropane (HCFC-243fa).

6. 2. The process of claim 1, wherein the propane in the feed comprises 1,3-dichloro-1,1,3-trifluoropropane (HCFC-243fb).

7. The catalyst is fluorinated Cr ２ O ３ , fluorinated Al ２ O ３ 10. The method of claim 1, further comprising one or more halide metal oxides selected from the group consisting of:

8. The catalyst is CrF ３ , AlF ３ , AlCl ３ , FeCl ３ , and FeCl ３ 2. The method of claim 1 , further comprising 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. 2. The process of claim 1, wherein the molar ratio of HF to propane in the feed ranges from 0.01:1 to 10:1.

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