Process for the catalytic conversion of a mixture of HCFO-1233zd(Z) and HCFC-244fa to HCFO-1233zd(E)

Abstract

To provide a method for producing mixtures containing HCFO-1233zd(Z) and HCFC-244fa that improves overall yields and reduces production cost.SOLUTION: There is provided a method for simultaneous conversion of a composition containing HCFO-1233zd(Z) and HCFC-244fa to form HCFO-1233zd(E), the method including the steps of: providing a composition including HCFO-1233zd(Z) and HCFC-244fa; and reacting the composition in a vapor phase in a reactor in presence of a chromium oxyfluoride catalyst to simultaneously isomerize HCFO-1233zd(Z) to form HCFO-1233zd(E) and dehydrohalogenate HCFC-244fa to form HCFO- 1233zd(E), wherein the reacting step is conducted at a temperature between 200°C and 250°C.SELECTED DRAWING: Figure 2

Description

[Background technology]

[0001] 1. Field of disclosure The present disclosure relates to (Z)-1-chloro-3,3,3-trifluoropropene (HCFO-12 33zd(Z), or 1233zd(Z)) and 1-chloro-1,3,3,3-tetrafluoroethylene (E)-1-chloropropane (HCFC-244fa or 244fa) mixture 3,3,3-trifluoropropene (HCFO-1233zd(E) or 1233 zd(E))

[0002] 2. Description of Related Technology (E)-1-chloro-3,3,3-trifluoropropene (HCFO-1233zd( 1233zd(E), or 1233zd(E), are new compounds with uses as blowing agents, solvents, and refrigerants. It is a low global warming and non-ozone depleting molecule. The uses and interests of this molecule are This has led to the development of several manufacturing processes for HCFO-1233 on a commercial scale. zd(E) is the 1,1,1,3,3-pentachlorodipropionate obtained by the reaction of HF with It is produced by fluorinating Pan (HCC-240fa), where (Z)-1 -Chloro-3,3,3-trifluoropropene (HCFO-1233zd(Z), or 1 233zd(Z)) is approximately 2% to 10% by weight of 1-chloro-1,3,3,3-tetrachloro- HCFO-123 along with fluoropropane (HCFC-244fa or 244fa) As a by-product in the ratio of 3zd(E) to HCFO-1233zd(Z) of approximately 10-20:1 Unfortunately, HCFO-1233zd(Z) and HCFC244fa are The formation results in reduced yield.

[0003] The fact that the boiling points of HCFO-1233zd(Z) and HCFC-244fa are similar means that the corresponding mixtures of these compounds exhibit azeotrope-like properties, and these two components cannot be separated by conventional distillation techniques. In addition, HCFO-1233zd(Z) has been applied as an alternative higher-boiling solvent, but HCFC-244fa is particularly toxic and makes it impossible to store mixtures of these compounds for long periods. As a result, the mixture of HCFC-244fa and HCFO-1233zd(Z) obtained from the commercial production of HCFO-1233zd(E) is typically transported to a thermal oxidizer for disposal, incurring additional manufacturing costs. Therefore, there is a growing need to develop production uses for the mixture of HCFC-244fa and HCFO-1233zd(Z) in order to reduce waste, improve overall yields, and lower manufacturing costs.

[0004] SUMMARY OF THE INVENTION The present disclosure provides a method for converting a composition containing HCFO-1233zd(Z) and HCFC-244fa into HCFO-1233zd(E) by reacting the mixture in the gas phase in the presence of a catalyst to isomerize HCFO-1233zd(Z) to form HCFO-1233zd(E) and simultaneously dehydrohalogenate HCFC-244fa to form HCFO-1233zd(E). The catalyst may be, for example, a chromium-based catalyst such as chromium trifluoride, chromium oxyfluoride, or chromium oxide.

[0005]

[0006] ​​​​​​​​ In one embodiment, the present invention is a method for simultaneously converting a composition containing HCFO-1233zd(Z) and HCFC-244fa to form HCFO-1233zd(E), comprising a step of feeding a mixture containing HCFO-1233zd(Z) and HCFC-244fa, and reacting the composition in the gas phase in a reactor in the presence of a chromium trifluoride (CrF3) catalyst to isomerize HCFO-1233zd(Z) to form HCFO-1233zd(E), and simultaneously dehydrohalogenating HCFC-244fa to form HCFO-1233zd(E). A method is provided that includes the above steps. (E).

[0007] The reaction step can be carried out at a temperature of 80°C to 250°C, or at a temperature of 100°C to 200°C. The contact time between the composition and the catalyst may be 1 second to 150 seconds, or may be 25 seconds to 125 seconds. The pressure in the reactor may be 25 psig to 100 psig.

[0008] During the reaction step, the reactor may contain less than 50 ppm of water. The reaction step can achieve a conversion rate of 88% to 96% of HCFO-1233zd(Z) to HCFO-1233zd(E), a conversion rate of 90% to 99% of HCFC-244fa to HCFO-1233zd(E), and / or a selectivity of 90% to 97% for HCFO-1233zd(E).

[0009] In the feeding step, the total impurities may be present in an amount less than 10% by weight, less than 6% by weight, or less than 1.5% by weight based on the total weight of the composition. When present in the composition, ​​Any HCFC-243fa and HCFC-243db may be present in an amount of less than 3 weight percent, based on the total weight of the composition.

[0010] After the reaction step, the method further includes, distilling the composition in a distillation column; removing an overhead stream from the distillation column, the overhead stream being concentrated in HCFO-1233zd(E); and removing a bottoms stream from the distillation column, the bottoms stream being concentrated in HCFO-1233zd(Z) and HCFC-244fa. The method may further include an additional step of recycling the bottoms stream to the reactor after the second removal step. BRIEF DESCRIPTION OF THE DRAWINGS

[0011] Referring to the following description of embodiments of the disclosure in conjunction with the accompanying drawings, the above and other features of the disclosure, and the manner in which they are accomplished, will become more readily apparent, and the disclosure itself will be better understood.

[0012]

Figure 1

Figure 2

[0013] Corresponding reference characters indicate corresponding parts throughout the several views. The drawings represent embodiments of various features and components in accordance with the disclosure, but the drawings are not necessarily to scale and certain features may be exaggerated to better illustrate and explain the disclosure. ​​​​Yes. The examples described in this specification illustrate embodiments of the present disclosure, and such examples should not be construed as limiting the scope of the invention in any way.

Mode for Carrying Out the Invention

[0014] The present disclosure provides a method for converting a composition containing HCFO-1233zd(Z) and HCFC-244fa into HCFO-1233zd(E) by reacting a mixture containing HCFO-1233zd(Z) and HCFC-244fa in the gas phase in the presence of a catalyst to isomerize HCFO-1233zd(Z) to form HCFO-1233zd(E) and simultaneously dehydrohalogenate HCFC-244fa to form HCFO-1233zd(E). The catalyst may be, for example, a chromium-based catalyst such as chromium trifluoride, chromium oxyfluoride, or chromium oxide.

[0015] Referring to FIG. 1, the isomerization of HCFO-1233zd(Z) (i.e., cis-HCFO-1233zd, or c-1233zd) to form HCFO-1233zd(E) (i.e., trans-HCFO-1233zd, or t-1233zd) is shown in reaction (i), and the dehydrohalogenation of HCFC-244fa to form HCFO-1233zd(E), hydrogen fluoride, and hydrogen chloride is shown in reaction (ii). According to the present disclosure, it has been found that both of the aforementioned reactions can be carried out simultaneously using the same catalyst. Specifically, the present disclosure introduces a manufacturing process for converting a mixture of HCFO-1233zd(Z) and HCFC-244fa into HCFO-1233zd(E) by heterogeneous gas-phase catalysis. ​​​​​​​​​​​​​​

[0016] A schematic diagram of the process for carrying out this reaction is shown in Figure 2. Input stream 10 containing HCFO-1233zd(Z ) and HCFC-244fa is provided to reactor 12. The HCFO-1233zd(Z) and HCFC-244fa in input stream 10 may be present in any desired amounts relative to each other and / or relative to the total weight of the mixture as a whole, but it may be desirable to limit the total amount of HCFC -244fa in input stream 10 to avoid the formation of certain by-products, as described below. Input stream 10 may itself be a fraction obtained from a commercial production process for preparing HCFO-1233zd(E). In this regard, input stream 10 may also contain any amount of HCFO-1233zd(E) that does not affect the conversion of HCFO-1233zd(Z) and HCFC-244fa present in input stream 10 to HCFO-1233zd(E). Alternatively, input stream 10 may be a recycle stream from the distillation column described below containing unreacted HCFO

[0017] -1233zd(Z) and HCFC-244fa. Input stream 10 may also be a combination as described above. Input stream 10 may also contain trace amounts of other impurities such as, for example, HCFC-243fa and HCFC-243db. Based on the total weight of the composition of stream 10, the presence of amounts of HCFC-243fa and HCFC-243db in the mixture of HCFO-1233zd(Z) and HCFC-244fa of less than 3% by weight has been found to have little or no significant effect on the product distribution. 33zd(Z) and HCFC-244fa. Alternatively, input stream 10 may be a recycle stream from the distillation column described below containing unreacted HCFO -1233zd(Z) and HCFC-244fa. Input stream 10 may also be a combination as described above. -1233zd(Z) and HCFC-244fa. Input stream 10 may also be a combination as described above. Input stream 10 may also be a combination as described above.

[0018] Input stream 10 may also contain trace amounts of other impurities such as, for example, HCFC-243fa and HCFC-243db. Based on the total weight of the composition of stream 10, the presence of amounts of HCFC-243fa and HCFC-243db in the mixture of HCFO-1233zd(Z) and HCFC-244fa of less than 3% by weight has been found to have little or no significant effect on the product distribution. -1233zd(Z) and HCFC-244fa. Input stream 10 may also be a combination as described above. HCFC-243db in the mixture of HCFO-1233zd(Z) and HCFC-244fa of less than 3% by weight has been found to have little or no significant effect on the product distribution. It has been found that the presence of amounts of HCFC-243fa and HCFC-243db in the mixture of HCFO-1233zd(Z) and HCFC-244fa of less than 3% by weight has little or no significant effect on the product distribution.

[0019] Impurities in the input stream 10, specifically HCFO-1233 in the input stream 10 The total amount of all compounds other than zd(Z), HCFC-244fa, and HCFO-1233zd(E) is less than 10 wt%, 8 wt% or less, 6 wt% or less, or even 1.5 wt% or less, based on the total weight of all compounds in the input stream. Higher concentrations of impurities are not desirable for long operating periods as they can potentially lead to a loss of catalytic activity over time. Larger amounts of impurities are not desirable for long operating periods as they can potentially lead to a loss of catalytic activity over time. Larger amounts of impurities are not desirable for long operating periods as they can potentially lead to a loss of catalytic activity over time.

[0020] In reactor 12, HCFO-1233zd(Z) and HCFC-244fa are vaporized and reacted in the gas phase in the presence of a catalyst such as a heterogeneous catalyst, which is a solid catalyst, in this reaction.

[0021] Suitable chromium-based catalysts include chromium oxide, chromium oxyfluoride, and chromium halide. Chromium oxide may include amorphous chromium oxide (Cr2O3), crystalline chromium oxide, and combinations thereof. Chromium oxyfluoride may include freshly pretreated amorphous chromium oxide (Cr2O3) with HF, freshly pretreated crystalline chromium oxide (Cr2O3) with HF, amorphous chromium oxyfluoride (Cr O F x O y F z where x may be 1 or 2, y may be 1 or 2, and z may be 1, 2, or 4), crystalline chromium oxyfluoride (Cr O x O y F z where x may be 1 or 2 and y may be 1 or 2, and z may be 1, 2, or 4), and combinations thereof. Examples include. In one embodiment, the catalyst is amorphous chromium oxyfluoride (Cr x O y F z , where x may be 1 or 2, y may be 1 or 2, and z may be 1 , 2, or 4). Examples of chromium halides include chromium trifluoride (CrF3 ), chromium trichloride (CrCl3), chromium triiodide (CrI3), and chromium tribromide (Cr Br3), and combinations thereof. In one embodiment, the catalyst is chromium trifluoride (CrF3).

[0022] In addition to chromium-based catalysts, other suitable catalysts include nickel fluoride, titanium fluoride, f molybdenum fluoride, cobalt fluoride, aluminum fluoride, and combinations of the foregoing, etc. other metal halides are included.

[0023] A suitable reaction temperature in reactor 12 is, for example, as low as 100 °C, 125 °C, 150 °C, 175 °C, or as high as 200 °C, 225 °C, 250 °C, or 275 °C, or 100 °C ~275 °C, 125 °C~250 °C, 150 °C~225 °C, or 175 °C~200 °C, etc. It may be within any range defined between any pair of the foregoing values.

[0024] Advantageously, when using chromium trifluoride (CrF3) as the catalyst, the isomerization and dehydrohalogenation reactions of the present invention can be carried out, for example, at 80 °C, 100 °C, or 125 °C, or as high as 175 °C, 200 °C, or 250 °C, or 80 °C~250 °C, 100 °C~20 0 °C, or 125 °C~175 °C, etc. within any range defined between any pair of the foregoing values to achieve effective conversion and selectivity at relatively low temperatures.

[0025] Suitable reaction pressures in reactor 12 can be, for example, as low as 0 psig, 25 psig, 50 psig or 75 psig, or 100 psig, 125 psig or higher 150psig, or 0psig~150psig, 25psig~125psig or Any range defined between any pair of the preceding values, such as 50 psig to 100 psig In one embodiment, the reaction pressure in the reactor is about 50 psig.

[0026] The amount of catalyst used can vary, but generally, the amount of catalyst in the stream 10 and in the reactor 12 is The contact time between the two may be as short as 1 second, 25 seconds, or 50 seconds, for example, or as long as If the time is longer than 1 second, it may be 100 seconds, 125 seconds, or 150 seconds, or it may be 1 second to 150 seconds, 25 Any pair of the above values, such as seconds to 125 seconds or 50 seconds to 100 seconds, It may be within the range.

[0027] The presence of water or water vapor in the reactor 12 can have a detrimental effect on the chromium-based catalyst and can cause rapid catalytic reaction. Therefore, the input stream and / or the The mixture may contain, for example, less than 0.0050% by weight (50 ppm) water, 0.0030% by weight (30 ppm) water, or less than 0.0020% by weight (20 ppm) water. stomach.

[0028] HCFO-1233zd(Z) and H to form HCFO-1233zd(E) can be produced during the simultaneous isomerization and dehydrohalogenation of CFC-244fa, respectively. One by-product is 1,1,1,3,3-pentafluoropropane (HFC-245fa ) is. The formation of HFC-245fa results in a yield reduction due to the potential formation of a binary azeotrope between HCFO-1233zd(E) and HFC-2 45fa. However when the reaction mixture contains less than 15 wt% of HCFC-244fa, the selectivity for the undesired byproduct HFC-245fa can be limited to less than 5%, as has been found .

[0029] In addition to HFC-245fa, hydrofluoric acid and hydrochloric acid are produced from the dehydro halogenation reaction of HCFC-244fa. Referring to Figure 2, these acids produced during the reaction can be neutralized, for example, by passing the product stream through a caustic scrubber 14 using a 10 wt% aqueous sodium hydroxide solution 16 without affecting the distribution of the product and byproducts, although other concentrations of other caustic (basic) solutions may be used. After passing through the caustic scrubber 14, the composition may be passed through a dryer 18 containing a desiccant suitable for removing moisture . .

[0030] In addition to HFC-245fa, other byproducts may include both isomers of HCFC-243fa and 1,3, 3,3-tetrafluoropropene (HFO-1234ze(Z) and HFO-1234ze(E)). Except for HFC-245fa, which has the potential to form a binary azeotrope with HCFO-1233zd(E), as shown in Figure 2, all other byproducts can be easily separated from the HCFO-1233zd(E ) product by a conventional upstream using a distillation column 20, in which the byproducts are removed either in the overhead stream 22 or the bottom stream 24 according to their boiling points . ) .

[0031] ​​​The HCFO-1233zd(E) product is concentrated in overhead stream 22, which is separated into bottoms stream 24. This means that more HCFO-1233zd(E) product is present in the overhead stream 22 than in the Any remaining unreacted HCFO-1233zd(Z) and HCFC-244fa are removed from the bottom of the column. Concentrated in stream 24 is more HCFO-1233zd(Z) and HCF than in overhead stream 22. C-244fa is present in bottoms stream 24. Optionally, unreacted HCFO-12 The 33zd(Z) and HCFC-244fa are returned to the reactor 12 via recycle stream 26. Good too.

[0032] Advantageously, the process comprises simultaneous isomerization of HCFO-1233zd(Z) and HCF HCFO-1233zd(Z) during the dehydrohalogenation of C-244fa Conversion to 1233zd(E) was greater than 88%, greater than 90%, greater than 93%, greater than 95%, and up to 96%. %, with simultaneous isomerization of HCFO-1233zd(Z) and HCFC-244 HCFC-244fa to HCFO-1233zd(E) during dehydrohalogenation of fa The conversion to is greater than 99%, 90%, greater than 92%, greater than 95%, greater than 97%, and up to 96% or It could be 99%.

[0033] In addition, the process simultaneously isomerizes HCFO-1233zd(Z) and HCFC- Selection against HCFO-1233zd(E) based on dehydrohalogenation of 244fa The selectivity may be greater than 90%, greater than 92%, greater than 95%, greater than 96%, up to 97%. EXAMPLES

[0034] Simultaneous isomerization and dehydrohalogenation using CrF3 catalyst HCFO-1233zd(Z), HCFC-244fa, and HCFO-1233zd Vaporize a feed stream consisting of (E) and react it over a CrF3 catalyst in the gas phase to produce HCFO- 1233zd(E). Specifically, a feedstock consisting of about 77 GC area % HCFO-1233z d(Z), 7.97 GC area % HCFC-244fa, and 13.89 GC area % H CFO-1233zd(E) was vaporized and fed to a 1-inch reactor containing 0.28 L of CrF3 pellets at a rate of 0.3 lb / hr (136 g / hr) and a reactor pressure of 50 psig. The reaction temperature was varied from 100 °C to 220 °C. The observed average productivity was 27.72 5 lb / hr (1.26 kg / hr) of HCFO-1233zd(E) per cubic foot (0.028 cubic meters) of CrF3 catalyst. Table 1 shows the average conversion of HCFO-1233zd(Z) and HCFC as a function of temperature, and the average selectivity to HCFO-1233zd(E) and by-products, using a CrF3 catalyst. C-244fa, as well as the average selectivity to HCFO-1233zd(E) and by-products.

[0035]

Table 1

Example

[0036] Simultaneous Isomerization and Dehydrohalogenation Using an Amorphous Chromium Oxyfluoride Catalyst HCFO-1233zd(Z), HCFC-244fa, and HCFO-1233zd (E) from a feed stream was vaporized and reacted over an amorphous chromium oxyfluoride catalyst in the gas phase to produce HCFO-1233zd(E). Specifically, about 91.70 GC area % ​HCFO-1233zd(Z), 7.99 GC area%, HCFC-244fa, and 0 .278 GC area% of HCFO-1233zd(E) was vaporized, and 0. At a rate of 3 lb / hr (136 g / hr) and a reactor pressure of 50 psig, it was fed to a 1-inch reactor containing 0.28 L of amorphous chromium oxyfluoride pellets. The reaction temperature was changed from 125 °C to 275°C. The observed average productivity was 24.7 lb / hr (11.21 kg / hr per cubic foot (0.028 cubic meters) of amorphous chromium oxyfluoride catalyst for HCFO-1233zd(E). Table 2 shows the average conversions of HCFO-1233zd(Z) and HCFC-244fa, and the average selectivities for HCFO-1233zd(E) and by-products as a function of temperature using an amorphous chromium oxyfluoride catalyst .

[0037]

Table 2

Example

[0038] Isomerization of HCFO-1233zd(Z) A feed stream consisting of HCFO-1233zd(Z) was vaporized and reacted over an amorphous chromium oxyfluoride catalyst in the gas phase to produce HCFO-1233zd(E). Specifically, a feed material consisting of more than 99.50 GC area% of HCFO-1233zd(Z) was vaporized and fed to a 1-inch reactor containing 0.28 L of amorphous chromium oxyfluoride pellets at a rate of 0.6 lb / hr (272 g / hr) and a reactor pressure of 50 pisg. The reaction temperature was maintained at 220°C to 230°C. The observed average productivity was for amorphous chromium oxyfluoride catalyst ​55.7 lb / hr (25.3 kg / hr) of HCFO-1233zd(E) per cubic foot (0.028 cubic meter) of catalyst was used. Table 3 shows the average conversion rate of HCFO-1233zd(Z) as a function of time with respect to the flow, and the average selectivity for HCFO-1233zd(E) and by-products using an amorphous chromium oxyfluoride catalyst .

[0039] **Table 3** **Examples**

[0040] Dehydrohalogenation of HCFC-244fa A feed stream consisting of HCFC-244fa was vaporized and reacted over an amorphous chromium oxyfluoride catalyst in the gas phase to produce HCFO-1233zd(E). Specifically, a feedstock consisting of >99 .50 GC area% HCFC-244fa was vaporized and fed to a 1-inch reactor containing 0.28 L of amorphous chromium oxyfluoride pellets at a rate of 0.3 lb / hr (136 g / hr) and a reactor pressure of 50 psig . The reaction temperature was maintained at 220°C to 230 °C. The observed average productivity was 18.2 lb / hr (8.3 kg / hr) of HCFO- 1233zd(E) per cubic foot (0.028 cubic meter) of amorphous chromium oxyfluoride catalyst . Table 4 shows the average conversion rate of HCFC-244fa as a function of time with respect to the flow, and the average selectivity for HCFO-123 3zd(E) and by-products using an amorphous chromium oxyfluoride catalyst .

[0041] **Table 4** ​​​

Example

[0042] Simultaneous isomerization and dehydrohalogenation of HCFC-243fa or HCFC-243db in the presence of an amorphous chromium oxyfluoride catalyst to produce HCFO-1233zd(Z), HCFC-244fa, HCFO-1233zd(E ) and a feed stream consisting of HCFC-243fa or HCFC-243db was vaporized and reacted in the gas phase over an amorphous chromium oxyfluoride catalyst to produce HCFO-1233zd(E). Specifically, a feedstock consisting of about 91.72 GC area% HCFO-1233zd(Z), 6. 55 GC area% HCFC-244fa, 0.07 GC area% HCFO-1233zd (E) and <3 GC area% HCFC-243fa or HCFC-243db was vaporized and fed at a rate of 0.3 lb / hr (136 g / hr) and a reactor pressure of 50 psig to a 1-inch reactor containing 0.28 L of amorphous chromium oxyfluoride pellets. The reaction temperature was maintained at 220 °C to 230 °C. The observed average productivity was 54.5 lb / hr (24.7 kg / hr) of HCFO-1233zd(E) per cubic foot (0.028 cubic meters) of amorphous chromium oxyfluoride catalyst. Table 5 shows the average conversion of HCFO-1233zd (Z), HCFC-244fa, HCFC-243fa, HCFC-243db as a function of time on stream, and the average selectivity to HCFO-1233zd(E) and by-products. (24.7 kg / hr) of HCFO-1233zd(E). Table 5 shows the average conversion of HCFO-1233zd (Z), HCFC-244fa, HCFC-243fa, HCFC-243db as a function of time on stream, and the average selectivity to HCFO-1233zd(E) and by-products. (Z), HCFC-244fa, HCFC-243fa, HCFC-243db as a function of time on stream, and the average selectivity to HCFO-1233zd(E) and by-products.

[0043]

Table 5

[0044] Although the present disclosure has been described as relating to exemplary designs, the present disclosure may be further modified within the spirit and scope of the present disclosure. Further, this application is intended to embrace such departures from the present disclosure as come within known or customary practice in the technical fields to which the invention pertains. This specification encompasses the following aspects of the invention. [1] A method for simultaneously converting a composition containing HCFO-1233zd(Z) and HCFC-244fa to form HCFO-1233zd(E), comprising the step of supplying a composition containing HCFO-1233zd(Z) and HCFC-244fa, reacting the composition in the gas phase in a reactor in the presence of a chromium trifluoride (CrF 3 ) catalyst to simultaneously isomerize HCFO-1233zd(Z) to form HCFO-1233zd(E) and dehydrohalogenate HCFC-244fa to form HCFO-1233zd(E). [2] The method according to [1], wherein the reaction step is carried out at a temperature of 80°C to 250°C. [3] The method according to [2], wherein the reaction step is carried out at a temperature of 100°C to 200°C. [4] The method according to [1], wherein the contact time between the composition and the catalyst is 1 second to 150 seconds. [5] The method according to [4], wherein the contact time between the composition and the catalyst is 25 seconds to 125 seconds. [6] The method according to [1], wherein the pressure in the reactor is 25 psig to 100 psig. [7] The method according to [1], wherein during the reaction step, the reactor contains less than 50 ppm of water. [8] The method according to [1], wherein the reaction step achieves a conversion of 88% to 96% of HCFO-1233zd(Z) to HCFO-1233zd(E). [9] The method according to [1], wherein the reaction step achieves a conversion of 90% to 99% of HCFC-244fa to HCFO-1233zd(E).

[10] The method according to [1], wherein the reaction step achieves a selectivity of 90% to 97% for HCFO-1233zd(E).

Claims

1. A method for simultaneously converting a composition comprising HCFO-1233zd(Z) and HCFC-244fa to form HCFO-1233zd(E), comprising: supplying a composition comprising HCFO-1233zd(Z) and HCFC-244fa; reacting the composition in the gas phase in a reactor in the presence of a chromium oxyfluoride catalyst to simultaneously isomerize HCFO-1233zd(Z) to form HCFO-1233zd(E) and dehydrohalogenate HCFC-244fa to form HCFO-1233zd(E); wherein the reaction step is carried out at a temperature of 200 °C to 250 °C; the reaction step achieves a selectivity of 90% to 97% for HCFO-1233zd(E); and the composition comprising HCFO-1233zd(Z) and HCFC-244fa comprises HCFC-244fa in an amount of 6.31% by weight or more and less than 15% by weight.

2. The method according to claim 1, wherein the contact time between the composition and the catalyst is from 1 second to 150 seconds.

3. The method according to claim 1, wherein the pressure in the reactor is from 0.101 MPa (0 psig) to 0.791 MPa (100 psig).

4. The method according to claim 1, wherein during the reaction step, the reactor contains less than 50 ppm of water.

5. The method according to claim 1, wherein in the feeding step, all impurities are present in an amount of less than 10% by weight based on the total weight of the composition.

6. The method according to claim 1, wherein in the feeding step, all compounds other than HCFO-1233zd(Z), HCFC-244fa and HCFO-1233zd(E) are present in an amount of less than 6% by weight based on the total weight of the composition.

7. After the reaction step, the following additional steps: distilling the composition in a distillation column; removing an overhead stream from the distillation column, the overhead stream being concentrated in HCFO-1233zd(E); and removing a bottoms stream from the distillation column, the bottoms stream being concentrated in HCFO-1233zd(Z) and HCFC-244fa. The method according to claim 1, further comprising the above steps.

8. The method according to claim 7, further comprising an additional step of recycling the bottoms stream to the reactor after the second removal step.

9. The method according to claim 1, wherein the reaction step is carried out at a temperature of 200 °C to 230 °C.

10. A method for simultaneously converting a composition containing HCFO-1233zd(Z) and HCFC-244fa to form HCFO-1233zd(E), comprising the step of feeding a composition containing HCFO-1233zd(Z) and HCFC-244fa, reacting the composition in the gas phase in a reactor in the presence of a chromium oxyfluoride catalyst to simultaneously isomerize HCFO-1233zd(Z) to form HCFO-1233zd(E) and dehydrohalogenate HCFC-244fa to form HCFO-1233zd(E), comprising, the reaction step achieving a selectivity to 92% to 97% of HCFO-1233zd(E), the reaction step being carried out at a temperature of 100°C to 275°C, and the composition containing HCFO-1233zd(Z) and HCFC-244fa containing 6.31% by weight or more and less than 15% by weight of HCFC-244fa. **Claim 11** The method according to claim 10, wherein the reaction step is carried out at a temperature of 200°C to 250°C. **Claim 12** The method according to claim 10, wherein the reaction step is carried out at a temperature of 200°C to 230°C.

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